Starch-based phch

ABSTRACT

The invention relates to a process for preparing self-binding pigment particle suspensions, to a self-binding pigment particle suspension as well as to a paper product comprising self-binding pigment particles and to the use of the self-binding pigment particle suspension in paper applications, such as in paper coating or as filler material.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.14/391,887, filed Oct. 10, 2014, which is the U.S. National Phase of PCTApplication No. PCT/EP2013/058884, filed Apr. 29, 2013, which claimspriority to U.S. Provisional Application No. 61/648,638, filed May 18,2012, and European Application No. 12167656.3, filed May 11, 2012, thecontents of which are hereby incorporated by reference.

The invention relates to a process for preparing self-binding pigmentparticle suspensions, to a self-binding pigment particle suspension aswell as to a paper product comprising self-binding pigment particles andto the use of the self-binding pigment particle suspension in paperapplications, such as in paper coating or as filler material.

Mineral materials and binders are among the main constituents used inthe manufacture of numerous products such as paints, paper and plasticmaterials. Therein, mineral materials such as calcium carbonate andother particulate materials contribute mechanical and opticalproperties, while the binder, generally latex-based and in the form ofaqueous suspensions or dispersions, provide the necessary adhesion andcohesion for the respective constituents of the end product to beproduced.

In order to avoid the logistic difficulties of handling mineralmaterials and binders separately, and further to avoid the unwantedphysical and chemical interactions developed in comparable mixtures ofmineral materials and binders, self-binding pigment particles have beendeveloped and are known to industry. In this regard, self-bindingpigment particles having both the properties of the mineral material andof the binder may be directly implemented in a variety of applications.This unique product named self-binding pigment particles refers todistinct, solid particles, formed of mineral material and binder thatare intimately bound to one another. The internal cohesion forces ofeach constituent component and the adhesion between them are such as toprovide the self-binding pigment particles with excellent mechanicalstability.

Self-binding pigment particles are prepared by a process implementing atleast one step of grinding mineral materials in the presence of binder,where grinding refers to an operation leading to a reduction in theparticle size; the mineral materials in the self-binding pigmentparticles have a smaller diameter than the initial mineral material usedto produce them. Such self-binding pigment particles are described in anumber of documents, including WO 2006/008657, WO 2006/128814, and WO2008/139292. Unpublished European Patent Application Number 11 160900.4describes a process for the preparation of self-binding pigmentparticles comprising the steps of: a) providing an aqueous mineralpigment suspension, b) providing at least one polymeric binder, whereinthe binder comprises at least one carboxymethylcellulose having a degreeof carboxylation in the range of 0.4 to 2.0 and having an intrinsicviscosity in the range of 3 to 300 ml/g, c) mixing the binder of step b)with the aqueous mineral pigment material suspension of step a) andadjusting the solids content of the obtained suspension so that it isfrom 45 to 80 wt.-%, based on the total weight of the suspension, and d)grinding the aqueous mineral material suspension of step c). UnpublishedEuropean Patent Application Number 11 160926.9 describes a process forpreparing of self-binding pigment particles comprising the steps of: a)providing an aqueous mineral pigment suspension, b) providing at leastone polymeric binder, wherein the binder comprises at least one modifiedpolysaccharide having a degree of carboxylation in the range of 0.4 to2.0 and having an intrinsic viscosity in the range of 3 to 300 ml/g,wherein the carbon of the binder shows a rate of nuclear transformationof ¹⁴C to ¹²C of between 900 and 920 transformations per hour and pergram carbon in the binder; c) mixing the binder of step b) with theaqueous mineral pigment material suspension of step a) and adjusting thesolids content of the obtained suspension so that it is from 45 to 80wt.-%, based on the total weight of the suspension, and d) grinding theaqueous mineral material suspension of step c) until the fraction ofself-binding pigment particles having a particle size of less than 1 μmis greater than 5 wt.-%, based on the total weight of the pigmentparticles, the foregoing and other objects are solved by thesubject-matter as defined herein in the present invention. Furthermore,EP 1 105 571 B1 refers to an additive composition for paper making to beadded to the pulp prior to web formation, said composition containing asits basic component components made from starch, the molecular size hasbeen reduced to effect a viscosity level of 10 to 400 mPas (5%, 60 C,Brookfield), and which has been cationized by solution, cationizingusing a quaternary nitrogen compound to a charge of <4 mEq/g and atleast one additional component, which is 1) a starch-based polymerdispersion which contains starch and a monomeric graft copolymer of,calculated on the dry-matter content of the product, a) 5 to 40% ofstarch, cationized to have a degree of substitution of 0.01 to 1 and anintrinsic viscosity of >1.0 dl/g, b) 60 to 95% of a monomer mixturecontaining at least one vinyl monomer and having a film formationtemperature of 0 to 70° C. of a polymer formed therefrom, and water, 2)polyamide epichlorhydrin resin (PAAE). Additionally, the applicant isaware of a trade product of Specialty Minerals Inc., Bethlehem, USA onthe international market called FulFill™ E-325, which is a large granuleof starch/PCC for higher filler loading of base paper. Due to thepresence of these coarse particle clusters having a particle size ofmore than 100 μm, no individual self-binding pigment particles areobserved. Paper filled with such coarse particle clusters is susceptibleto dusting and coating scratches. The article “Improvement of paperproperties using starch-modified precipitated calcium carbonate filler”of Zhao et al., TAPPI Journal 2005, vol. 4(2), is concerned withcommercial precipitated calcium carbonate fillers that have beenmodified with corn and potato raw starches. These modified fillers wereused as papermaking fillers to improve the strength in high fillercontent papers.

For completeness, the Applicant would like to mention the followingapplications in its name, which also refer to processes for preparingself-binding pigment particles: unpublished European Patent Applicationswith filing numbers 11 160900.4, 11 160926.9, 11 179604.1 and 11179572.0.

However, there is one specific problem which very often has significantimpact on the mechanical and optical properties of paper coatings madefrom such self-binding pigment particles. As set out above, self-bindingpigment particles contain an intimate combination of mineral materialand binder, which are typically provided in form of an aqueoussuspension. The provision of a self-binding pigment particle suspension,however, often results in paper coatings imparting not well-adjustedmechanical and optical properties to the corresponding end product. Moreprecisely, the mechanical and optical properties are worsened due to thepresence of high amounts of free dissolved binder in the coating colorand the subsequent paper product coated with such a coating color.Consequently, a high amount of free dissolved binder in the self-bindingpigment particle suspension provides significantly decreased mechanicaland optical properties to the end product. The resulting poor propertiesare especially detrimental for applications in the field of papercoatings as well as paints and plastics.

Thus, there is still a need in the art for providing a process whichavoids the foregoing disadvantages and especially allows for improvingthe mechanical and optical properties of a coating resulting fromself-binding pigment particles being derived from a suspension ofself-binding pigment particles. In other words, it would be desirable toprovide a method which leads to self-binding pigment particlesuspensions wherein the resulting paper product coated with saidsuspension has higher mechanical and optical properties compared toprior art methods.

Accordingly, it is an objective of the present invention to provide aprocess for preparing a self-binding pigment particle suspension whereinthe resulting paper coating of said suspension has improved mechanicaland optical properties and especially a reduced content of freedissolved binder. Further objectives can be gathered from the followingdescription of the invention.

According to a first aspect of the present invention, a process forpreparing self-binding pigment particles, comprising the following stepsof:

-   a) providing an aqueous pigment material suspension;-   b) providing at least one anionic and/or amphoteric starch;-   c) mixing the starch of step b) with the aqueous pigment material    suspension of step a), wherein the starch is added to the aqueous    pigment material suspension in an amount from 0.5 to 20 wt.-%, based    on the total weight of the dry pigment in the suspension, and-   d) combining the aqueous pigment material particles and starch of    step c) by grinding such that the amount of free starch in the    obtained suspension is less than 50 wt.-% based on the total amount    of starch added in step c) and the pigment material surface charge    after step d) is neutral or anionic.

The inventors surprisingly found that the foregoing process according tothe present invention leads to a self-binding pigment particlesuspension providing mechanical and optical properties to paper coatingsmade thereof being higher than the mechanical and optical properties ofa corresponding coating prepared from a self-binding pigment particlesuspension being treated the same way but without contacting it withsaid at least one anionic and/or amphoteric starch (step c)).

It should be understood that for the purposes of the present invention,the following terms have the following meaning:

The term aqueous “pigment material” suspension in the meaning of thepresent invention encompasses natural and/or synthetic materials, likecalcium carbonate, talc, chalk, dolomite, mica, titanium dioxide etc.

The term aqueous pigment material “suspension” in the meaning of thepresent invention comprises insoluble solids and water and optionallyfurther additives and usually contains large amounts of solids and,thus, is more viscous and generally of higher density than the liquidfrom which it is formed.

The term “starch” in the meaning of the present invention refers topolymeric carbohydrate structures, formed by a plurality of glucoseunits joined together by glycosidic bonds. These structures may belinear, but may also contain various degrees of branching.

The term “anionic” in the meaning of the present invention refers to acompound having a net negative charge. Said compound is typicallymodified with anionic groups. The term “anionic” does not exclude thepresence of cationic groups provided that the sum of individual chargesis negative.

The term “amphoteric” or “neutral” in the meaning of the presentinvention refers to a compound modified with anionic groups as well ascationic groups such that the number of negative charges in the anionicgroups is about equal to the number of positive charges in the cationicgroups.

The term “free starch” in the meaning of the present invention refers tothe amount of starch in the liquid phase of the self-binding pigmentparticle suspension passing a membrane filter having a pore size of 0.2micron.

Where the term “comprising” is used in the present description andclaims, it does not exclude other elements. For the purposes of thepresent invention, the term “consisting of” is considered to be apreferred embodiment of the term “comprising of”. If hereinafter a groupis defined to comprise at least a certain number of embodiments, this isalso to be understood to disclose a group, which preferably consistsonly of these embodiments.

Where an indefinite or definite article is used when referring to asingular noun, e.g. “a”, “an” or “the”, this includes a plural of thatnoun unless something else is specifically stated.

Terms like “obtainable” or “definable” and “obtained” or “defined” areused interchangeably. This e.g. means that, unless the context clearlydictates otherwise, the term “obtained” does not mean to indicate thate.g. an embodiment must be obtained by e.g. the sequence of stepsfollowing the term “obtained” even though such a limited understandingis always included by the terms “obtained” or “defined” as a preferredembodiment.

Another aspect of the present invention is directed to a self-bindingpigment particle suspension obtainable by the process.

A further aspect of the present invention is directed to a paper productcomprising self-binding pigment particles, wherein the pigment particlesare at least partially coated with at least one anionic and/oramphoteric starch.

A still further aspect of the present invention is directed to the useof the self-binding pigment particle suspension in paper applicationssuch as in paper coating. It is preferred that the self-binding pigmentparticle suspension is used in paper coating applications as a supportfor rotogravure and/or offset and/or digital printing and/or flexographyand/or decoration surfaces. Another aspect of the present invention isdirected to the use of the self-binding pigment particle suspension inpaper applications such as filler material. It is preferred that thefiller material is used in plastics, paint, concrete and/or agriculturalapplications. It is also preferred that the self-binding pigmentparticle suspension is used to reduce sun light and UV exposure of plantleaves.

When in the following reference is made to preferred embodiments ortechnical details of the inventive process for preparing self-bindingpigment particle suspensions, it is to be understood that thesepreferred embodiments and technical details also refer to the inventiveself-binding pigment particle suspension, the inventive paper productcomprising a pigment material as well as to the use of the self-bindingpigment particle suspension defined herein and vice versa (as far asapplicable). If, for example, it is set out that the aqueous pigmentmaterial suspension provided in the process for preparing self-bindingpigment particle suspensions comprises a pigment material selected fromthe group comprising calcium carbonate, calcium carbonate containingminerals, mixed carbonate based fillers, or mixtures thereof, also theinventive self-binding pigment particle suspension, the inventive paperproduct comprising a pigment material as well as the use of theself-binding pigment particle suspension preferably comprise a pigmentmaterial selected from the group comprising calcium carbonate, calciumcarbonate containing minerals, mixed carbonate based fillers, ormixtures thereof.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the pigmentmaterial suspension of step a) comprises a pigment material selectedfrom the group comprising calcium carbonate, calcium carbonatecontaining minerals, mixed carbonate based fillers, or mixtures thereof,and wherein the calcium carbonate containing minerals preferablycomprise dolomite, and the mixed carbonate based fillers are preferablyselected from calcium associated with magnesium, clay, talc,talc-calcium carbonate mixtures, calcium carbonate-kaolin mixtures, ormixtures of natural calcium carbonate with aluminium hydroxide, mica orwith synthetic or natural fibers or co-structures of minerals,preferably talc-calcium carbonate or talc-titanium dioxide or calciumcarbonate-titanium dioxide co-structures.

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the calciumcarbonate is a ground natural calcium carbonate, a precipitated calciumcarbonate, a modified calcium carbonate, or a mixture thereof.

According to yet another preferred embodiment of the inventive processfor preparing self-binding pigment particle suspensions, the at leastone starch of step b) is an anionic starch comprising anionic groupsselected from the group comprising carboxyl groups, carboxymethylgroups, carboxymethyl hydroxypropyl groups, carboxymethyl hydroxyethylgroups, phosphate groups, sulfonate groups and mixtures thereof,preferably the anionic group is selected from carboxyl groups andcarboxymethyl groups

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the at least onestarch of step b) is an anionic starch having a degree of carboxylationin the range of 0.001 to 0.08, preferably in the range of 0.0025 to0.06, more preferably in the range of 0.0025 to 0.05 and most preferablyin the range of 0.008 to 0.05.

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the at least onestarch of step b) is an amphoteric starch comprising anionic groupsselected from the group comprising carboxyl groups, carboxymethylgroups, carboxymethyl hydroxypropyl groups, carboxymethyl hydroxyethylgroups, phosphate groups, sulfonate groups and mixtures thereof andcationic groups selected from the group comprising amino groups,immonium groups, ammonium groups, sulfonium groups, phosphonium groupsand mixtures thereof, preferably the anionic group is selected fromcarboxyl groups and carboxymethyl groups, and the cationic group isselected from tertiary amino groups and quaternary ammonium groups.

According to yet another preferred embodiment of the inventive processfor preparing self-binding pigment particle suspensions, the at leastone starch of step b) has a ratio between the degree of anionicsubstitution and the degree of cationic substitution (DS_(a)/DS_(c)) ofthe hydroxyl groups of more than 0.8, preferably of more than 0.9 andmost preferably equal 1.0.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the at least onestarch of step b) is in form of a starch solution or a starch suspensionor a dry material, preferably in form of a starch suspension.

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the at least onestarch of step b) is in form of a starch solution or starch suspensionhaving a starch concentration from 1 wt.-% to 50 wt.-%, preferably from10 wt.-% to 50 wt.-%, more preferably from 15 wt.-% to 45 wt.-% and mostpreferably from 20 wt.-% to 45 wt.-%, based on the total weight of thestarch solution or starch suspension.

According to yet another preferred embodiment of the inventive processfor preparing self-binding pigment particle suspensions, in step c) theat least one starch is added to the aqueous pigment material suspensionin an amount from 1 to 20 wt.-%, preferably 1 to 19 wt.-%, morepreferably 1 to 18 wt.-%, based on the total weight of the dry pigmentmaterial in the aqueous pigment material suspension.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the solids contentin step c) is adjusted such that it is at least 1 wt.-%, preferably from1 wt.-% to 80 wt.-%, more preferably from 5 wt.-% to 60 wt.-%, even morepreferably from 10 wt.-% to 50 wt.-% and most preferably from 15 wt.-%to 45 wt.-%, based on the total weight of the aqueous pigment materialsuspension.

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, grinding step d) iscarried out during and/or after step c), preferably during step c).

According to yet another preferred embodiment of the inventive processfor preparing self-binding pigment particle suspensions, grinding stepd) is carried out at a temperature from 10° C. to 40° C., preferablyfrom 20° C. to 40° C. and most preferably from 20° C. to 30° C., e.g. atroom temperature.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, grinding step d) iscarried out until the fraction of self-binding pigment particles havinga particle size of less than 1 μm is greater than 10 wt.-%, preferablygreater than 30 wt.-%, more preferably greater than 50 wt.-%, and mostpreferably greater than 70 wt.-%, based on the total weight of thepigment particles and/or until the fraction of self-binding pigmentparticles having a particle size of less than 2 μm is greater than 20wt.-%, preferably greater than 40 wt.-%, more preferably greater than 60wt.-%, and most preferably greater than 80 wt.-%, based on the totalweight of the pigment particles.

According to yet another preferred embodiment of the inventive processfor preparing self-binding pigment particle suspensions, the pigmentmaterial in the obtained self-binding pigment particle suspension has asurface charge density in the range of +2.5 μEq/g and −10 μEq/g, morepreferably in the range of +2 μEq/g and −8 μEq/g and most preferably inthe range of +0.5 μEq/g and −6 μEq/g.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, the obtainedself-binding pigment particle suspension has a Brookfield viscosity inthe range of 1 to 3 500 mPas, preferably in the range of 10 to 3 000mPas, more preferably in the range of 50 to 2 500 mPas and mostpreferably in the range of 50 to 2 000 mPas.

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, grinding step c) iscarried out such that the amount of free starch in the obtainedself-binding pigment particle suspension is less than 45 wt.-%,preferably less than 40 wt.-% and most preferably less than 35 wt.-%,based on the total amount of starch added in step c).

According to yet another preferred embodiment of the inventive processfor preparing self-binding pigment particle suspensions, the processfurther comprises step e) of concentrating the obtained self-bindingpigment particle suspensions such that the solids content in thesuspension is at least 45 wt.-%, preferably from 45 wt.-% to 80 wt.-%,more preferably from 50 wt.-% to 80 wt.-% and most preferably from 55wt.-% to 79 wt.-%, based on the total weight of the self-binding pigmentparticle suspension.

According to one preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, concentration stepe) is carried out before or after step d).

According to another preferred embodiment of the inventive process forpreparing self-binding pigment particle suspensions, before or during orafter step c) and/or step d) a dispersing agent is added.

As set out above, the inventive process for preparing self-bindingpigment particle suspensions comprises the steps a), b), c) and d). Inthe following, it is referred to further details of the presentinvention and especially the foregoing steps of the inventive processfor preparing self-binding pigment particle suspensions.

Step a): Provision of an Aqueous Pigment Material Suspension

According to step a) of the process of the present invention, an aqueouspigment material suspension is provided.

The aqueous pigment material suspension is obtained by mixing aparticulate pigment material with water. The pigment material to beprocessed according to the inventive process may be selected fromcalcium carbonate, calcium carbonate containing minerals, mixedcarbonate based fillers, or mixtures thereof.

According to a preferred embodiment of the present invention, thepigment material is a calcium carbonate. Calcium carbonate may be aground natural calcium carbonate, also named heavy calcium carbonate, aprecipitated calcium carbonate, also named light calcium carbonate, amodified calcium carbonate or a mixture thereof.

“Ground natural calcium carbonate” (GNCC) in the meaning of the presentinvention is a calcium carbonate obtained from natural sources, such aslimestone, marble, chalk and mixtures thereof, and processed through awet and/or dry treatment such as grinding, screening and/orfractionating, for example by a cyclone or classifier.

“Modified calcium carbonate” (MCC) in the meaning of the presentinvention may feature a natural ground or precipitated calcium carbonatewith an internal structure modification or a surface-reaction product.According to a preferred embodiment of the present invention, themodified calcium carbonate is a surface-reacted calcium carbonate.

“Precipitated calcium carbonate” (PCC) in the meaning of the presentinvention is a synthesized material, generally obtained by precipitationfollowing the reaction of carbon dioxide and lime in an aqueousenvironment or by precipitation of a calcium and carbonate source inwater or by precipitation of calcium and carbonate ions, for exampleCaCl₂ and Na₂CO₃, out of solution. Precipitated calcium carbonate existsin three primary crystalline forms: calcite, aragonite and vaterite, andthere are many different polymorphs (crystal habits) for each of thesecrystalline forms. Calcite has a trigonal structure with typical crystalhabits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonalprismatic, pinacoidal, colloidal (C-PCC), cubic, and prismatic (P-PCC).Aragonite is an orthorhombic structure with typical crystal habits oftwinned hexagonal prismatic crystals, as well as diverse assortment ofthin elongated prismatic, curved bladed, steep pyramidal, chisel shapedcrystals, branching tree, and coral or worm-like form.

In one preferred embodiment of the inventive process, the pigmentmaterial comprises a mixture of ground natural calcium carbonate, aprecipitated calcium carbonate or a modified calcium carbonate. Forexample, if the pigment material comprises a mixture of ground naturalcalcium carbonate, the pigment material comprises a mixture of at leasttwo pigment materials selected from limestone, marble and chalk.According to one embodiment of the present invention, the calciumcarbonate-containing mineral comprises dolomite.

According to a preferred embodiment, the mixed carbonate based fillersare selected from calcium associated with magnesium and analogues orderivatives, various matter such as clay or talc or analogues orderivatives, and mixtures of these fillers, such as, for example,talc-calcium carbonate or calcium carbonate-kaolin mixtures, or mixturesof natural calcium carbonate with aluminium hydroxide, mica or withsynthetic or natural fibers or co-structures of minerals such astalc-calcium carbonate or talc-titanium dioxide or calciumcarbonate-titanium dioxide co-structures.

The particulate pigment material of the aqueous pigment materialsuspension provided in step a) may have a particle size distribution asconventionally employed for the material(s) involved in the type ofproduct to be produced. In general, it is preferred that the pigmentmaterial particles in the suspension have a weight median particlediameter d₅₀ value of from 0.05 μm to 100 μm, preferably from 0.1 μm to60 μm and more preferably from 0.2 μm to 20 μm, most preferably from 0.3μm to 10 μm, for example from 0.4 μm to 1 μm as measured using aSedigraph™ 5120 of Micromeritics Instrument Corporation.

The value d_(x) represents the diameter relative to which x % by weightof the particles have diameters less than d_(x). This means that the d₂₀value is the particle size at which 20 wt.-% of all particles aresmaller, and the d₇₅ value is the particle size at which 75 wt.-% of allparticles are smaller. The d₅₀ value is thus the weight median particlesize at which 50 wt.-% of all particles are bigger or smaller than thisparticle size. The method and the instrument are known to the skilledperson and are commonly used to determine grain size of fillers andpigments. The measurement is carried out in an aqueous solution of 0.1wt.-% Na₄P₂O₇. The samples are dispersed using a high speed stirrer andsupersonics.

In a preferred embodiment, the pigment material particles in thesuspension exhibit a BET specific surface area of from 0.1 m²/g to 200m²/g, more preferably 3 m²/g to 25 m²/g, most preferably 5 m²/g to 20m²/g and even more preferably 6 m²/g to 15 m²/g, measured using nitrogenand the BET method according to ISO 9277.

The pigment material particles of the present invention are suspended inwater and thus form an aqueous suspension or slurry of pigment material.

Preferably, the aqueous pigment material suspension provided in step a)has a solids content from 1 wt.-% to 80 wt.-%, preferably from 5 wt.-%to 60 wt.-%, more preferably from 10 wt.-% to 50 wt.-% and mostpreferably from 15 wt.-% to 45 wt.-%, based on the total weight of theaqueous pigment material suspension.

The aqueous pigment material suspension provided in step a) preferablyhas a temperature of ≤40° C., preferably between 5° C. and 40° C., morepreferably between 10° C. and 40° C. and most preferably between 15° C.and 30° C. For example, the aqueous pigment material suspension isprovided at about room temperature.

In one preferred embodiment of the present invention, the aqueouspigment material suspension provided in step a) has a temperature ofbetween 15° C. and 30° C. For example, the aqueous pigment materialsuspension provided in step a) has a temperature of about roomtemperature.

Step b): Provision of at Least One Amphoteric and/or Anionic Starch

According to step b) of the process of the present invention, at leastone amphoteric and/or anionic starch is provided.

In one preferred embodiment of the present invention, the at least oneamphoteric and/or anionic starch is composed of only one type of starch.In another preferred embodiment of the present invention, the at leastone amphoteric and/or anionic starch is composed of a mixture of two ormore types of starch. For example, the at least one amphoteric and/oranionic starch is composed of a mixture of two or more types ofamphoteric starch or the at least one amphoteric and/or anionic starchis composed of a mixture of two or more types of anionic starch.Alternatively, the at least one amphoteric and/or anionic starch iscomposed of a mixture of two or more types of amphoteric and anionicstarches.

According to the present invention, the at least one amphoteric and/oranionic starch is a homopolysaccharide. Preferably, thehomopolysaccharide is composed of a plurality of repeating units (atleast 10) of glucose. More preferably, the homopolysaccharide is alinear chain of 1,4-linked α-D-glucopyranosyl units.

Additionally or alternatively, the homopolysaccharide comprisesα-D-glucopyranosyl units which are 1,6-linked to the linear chain of1,4-linked α-D-glucopyranosyl units. In one preferred embodiment, the1,6-linked α-D-glucopyranosyl units are also linked to a linear chain of1,4-linked α-D-glucopyranosyl units.

Preferably, the at least one amphoteric and/or anionic starch of thepresent invention comprises amylose and/or amylopectin fractions. Inthis regard, it is preferred that the at least one amphoteric and/oranionic starch of the present invention is a dextrin.

The term “dextrin” in the meaning of the present invention refers to acarbohydrate product obtained by thermally degrading starch. Theobtained thermally modified starch has a lower molecular weight comparedto the starch before the thermal degradation. For example, more than 95wt.-% of the dextrin has a molecular weight of below 1 000 000 g/mol,more preferably more than 96 wt.-% of the dextrin has a molecular weightof below 1 000 000 g/mol and most preferably, more than 97 wt.-% of thedextrin has a molecular weight of below 1 000 000 g/mol, based on thetotal weight of the dextrin. Preferably, more than 60 wt.-% of thedextrin has a molecular weight between 5 000 g/mol and 200 000 g/mol,more preferably more than 65 wt.-% of the dextrin has a molecular weightbetween 5 000 g/mol and 200 000 g/mol and most preferably more than 69wt.-% of the dextrin has a molecular weight between 5 000 g/mol and 200000 g/mol, based on the total weight of the dextrin. For example,between 30 and 40 wt.-% of the dextrin has a molecular weight between 5000 g/mol and 25 000 g/mol and between 30 and 40 wt.-% of the dextrinhas a molecular weight between 25 000 g/mol and 200 000 g/mol, based onthe total weight of the dextrin. Preferably, between 32.5 and 37.5 wt.-%of the dextrin has a molecular weight between 5 000 g/mol and 25 000g/mol and between 32.5 and 37.5 wt.-% of the dextrin has a molecularweight between 25 000 g/mol and 200 000 g/mol, based on the total weightof the dextrin.

The starches used to obtain the at least one amphoteric and/or anionicstarch can be of any desired origin, provided that the at least onestarch contains free hydroxyl groups which can be modified.

The term “modified” or “modified starch” in the meaning of the presentinvention refers to a starch and/or dextrin (thermally modified starch),wherein at least a part of the hydroxyl groups is replaced by anionicand/or cationic groups.

The at least one amphoteric and/or anionic starch can advantageously bechosen from amongst the native starches and/or chemically modifiedstarches and/or thermally modified starches originated from starchesselected from the group comprising wheat starch, corn starch, ricestarch, potato starch, tapioca starch, maranta starch, sorghum starchand mixtures thereof. In one preferred embodiment of the presentinvention, the at least one amphoteric and/or anionic starch is nativestarch selected from the group comprising rice starch, potato starch andmixtures thereof. In another preferred embodiment of the presentinvention, the at least one amphoteric and/or anionic starch ischemically modified starch selected from the group consisting of ricestarch, potato starch and mixtures thereof. In a further preferredembodiment of the present invention, the at least one amphoteric and/oranionic starch is thermally modified corn starch, e.g. a dextrin.

One specific requirement of the present invention is that the starchprovided in the inventive process is at least one amphoteric and/oranionic starch.

If the at least one amphoteric and/or anionic starch is an anionicstarch, the starch is preferably chemically modified with anionic groupsselected from the group comprising carboxyl groups, carboxymethylgroups, carboxymethyl hydroxypropyl groups, carboxymethyl hydroxyethylgroups, phosphate groups, sulfonate groups and mixtures thereof.

In one preferred embodiment of the present invention, the starch ischemically modified with anionic groups selected from carboxyl groupsand carboxymethyl groups.

Methods for preparing such anionic starches are known to the skilledperson.

In one preferred embodiment, the at least one anionic starch has adegree of carboxylation in the range of 0.001 to 0.08, preferably in therange of 0.0025 to 0.06, more preferably in the range of 0.0025 to 0.05and most preferably in the range of 0.008 to 0.05.

Additionally or alternatively, the at least one amphoteric and/oranionic starch is an amphoteric starch.

Preferably, if the at least one amphoteric and/or anionic starch is anamphoteric starch, the starch is chemically modified with anionic groupsselected from the group comprising carboxyl groups, carboxymethylgroups, carboxymethyl hydroxypropyl groups, carboxymethyl hydroxyethylgroups, phosphate groups, sulfonate groups and mixtures thereof.Additionally, the at least one amphoteric starch is chemically modifiedwith cationic groups selected from the group comprising amino groups,immonium groups, ammonium groups, sulfonium groups, phosphonium groupsand mixtures thereof.

For example, the at least one amphoteric starch is chemically modifiedwith anionic groups selected from carboxyl groups and carboxymethylgroups. Additionally, the at least one amphoteric starch is chemicallymodified with cationic groups selected from tertiary amino groups andquaternary ammonium groups.

In one preferred embodiment, the at least one amphoteric starch ischemically modified with carboxymethyl groups as anionic groups andquaternary ammonium groups as cationic groups.

Methods for preparing such amphoteric starches are known to the skilledperson.

Preferably, the at least one amphoteric starch is chemically modifiedwith anionic groups as well as cationic groups such that the ratiobetween the degree of anionic substitution and the degree of cationicsubstitution (DS_(a)/DS_(c)) of the hydroxyl groups is more than 0.8 andpreferably more than 0.9. In one especially preferred embodiment of thepresent invention, the hydroxyl groups of the at least one amphotericstarch are chemically modified with anionic groups as well as cationicgroups such that the ratio between the degree of anionic substitutionand the degree of cationic substitution (DS_(a)/DS_(c)) of the hydroxylgroups is equal 1.0.

Additionally or alternatively, the at least one amphoteric starch ischemically modified with anionic groups as well as cationic groups suchthat the ratio of the anionic charge to the cationic charge lies in therange from 55:45 to 45:55 Mol-%, more preferably in the range from 53:47to 47:53 Mol-% and most preferably in the range from 51:49 to 49:51Mol-%.

Suitable anionic and/or amphotheric starches are available from a widevariety of commercial sources. Useful anionic and/or amphothericstarches include the starches available from Cargill, Switzerland asC*icoat 07525 and C*Film 07311. Furthermore, useful anionic and/oramphotheric starches include also the starches available fromSigma-Aldrich, Switzerland as S7260 and S03967 and from Avebe U.A., TheNetherlands as Perfectacote 35.

In one preferred embodiment of the present invention, the at least oneamphoteric and/or anionic starch is provided in form of a starchsolution or a starch suspension or a dry material. For example, the atleast one amphoteric and/or anionic starch is provided in form of astarch suspension.

The term “starch solution” in the meaning of the present inventionrefers to a system comprising solvent and starch, wherein the particlesof the at least one amphoteric and/or anionic starch are dissolved inthe solvent. The term “dissolved” in the meaning of the presentinvention refers to systems in which no discrete solid particles areobserved in the solvent, i.e. the at least one polysaccharide forms ahydrocolloidal solution.

The term “starch suspension” in the meaning of the present inventionrefers to a system comprising solvent and starch, wherein at least apart of the particles of the at least one amphoteric and/or anionicstarch are present as insoluble solids in the solvent. Said term doesnot exclude that a part of the at least one amphoteric and/or anionicstarch is dissolved in the solvent.

If the at least one amphoteric and/or anionic starch is provided in formof a starch solution, the solution can be in form of an aqueoussolution, i.e. the at least one amphoteric and/or anionic starch isprovided in water. Alternatively, the starch solution can be in form ofan organic solution, i.e. the at least one amphoteric and/or anionicstarch is provided in an organic solvent selected from the groupcomprising methanol, ethanol, acetone and mixtures thereof.

If the at least one amphoteric and/or anionic starch is provided in formof a starch solution, the solution is preferably prepared in that the atleast one amphoteric and/or anionic starch is added to a solvent,preferably water, having a temperature of ≤40° C., preferably between 5°C. and 40° C., more preferably between 10° C. and 40° C. and mostpreferably from 15° C. to 30° C. For example, the solution is preparedin that the at least one amphoteric and/or anionic starch is added towater having about room temperature.

Alternatively, the at least one amphoteric and/or anionic starch isprovided in form of a starch suspension, which may be preferablyprepared in that the at least one amphoteric and/or anionic starch isadded to a solvent, preferably water, having a temperature of ≤40° C.,preferably between 5° C. and 40° C., more preferably between 10° C. and40° C. and most preferably from 15° C. to 30° C.

In one preferred embodiment, the starch suspension is prepared in thatthe at least one amphoteric and/or anionic starch is added to water atabout room temperature.

In one preferred embodiment of the present invention, the at least oneamphoteric and/or anionic starch is in form of a starch solution orstarch suspension having a starch concentration ranging from 1 wt.-% to50 wt.-%, preferably from 10 wt.-% to 50 wt.-%, more preferably from 15wt.-% to 45 wt.-% and most preferably from 20 wt.-% to 45 wt.-%, basedon the total weight of the starch solution or starch suspension.

If the at least one amphoteric and/or anionic starch is provided in formof a starch suspension, the suspension preferably comprises an amount ofdissolved starch of less than 50 wt.-%, based on the total amount ofstarch added to the starch suspension. Preferably, the starch suspensionpreferably comprises an amount of dissolved starch of less than 40wt.-%, preferably less than 35 wt.-% and most preferably less than 30wt.-%, based on the total amount of starch in the starch suspension.

Additionally or alternatively, the starch suspension preferablycomprises an amount of insoluble starch in the solvent of more than 50wt.-%, based on the total amount of starch added to the starchsuspension. Preferably, the starch suspension preferably comprises anamount of insoluble starch in the solvent of more than 60 wt.-%,preferably more than 65 wt.-% and most preferably more than 70 wt.-%,based on the total amount of starch in the starch suspension.

It is generally considered that the initial viscosity (before mixing thestarch with the aqueous pigment material suspension in step c)) of thestarch solution or starch suspension of the present invention issatisfactory with respect to the envisaged use. In particular, thestarch solution or starch suspension has a Brookfield viscosity,measured at 25° C., 23-23.8° C. and 100 rpm with SPDL 2, except forPotato starch (e.g. 03967 of Fluka (Sigma-Aldrich)) which was measuredwith SPDL 5, in the range of 1 to 2 500 mPas, preferably in the range of10 to 2 000 mPas, more preferably in the range of 20 to 1 500 mPas, evenmore preferably in the range of 20 to 1 000 mPas and most preferably inthe range of 50 to 500 mPas.

Step c): Mixing the at Least One Starch with the Aqueous PigmentMaterial Suspension

According to step c) of the process of the present invention, the atleast one amphoteric and/or anionic starch of step b) is mixed with theaqueous pigment material suspension of step a).

In accordance with the present invention, the at least one amphotericand/or anionic starch is added to the aqueous pigment materialsuspension in an amount from 0.5 to 20 wt.-%, based on the total weightof the dry pigment material in the aqueous pigment material suspension.

In one preferred embodiment of the present invention, the at least oneamphoteric and/or anionic starch is added to the aqueous pigmentmaterial suspension in an amount from 1 to 20 wt.-%, preferably 1 to 19wt.-% and most preferably 1 to 18 wt.-%, based on the total weight ofthe dry pigment material in the aqueous pigment material suspension.

The amount of the at least one amphoteric and/or anionic starch in thesuspension can be adjusted by methods known to the skilled person. Toadjust the amount of starch in the suspension, the suspension may bepartially or fully dewatered by a filtration, centrifugation or thermalseparation process. For example, the suspension may be partially orfully dewatered by a filtration process such as nanofiltration or athermal separation process such as an evaporation process.Alternatively, water may be added to the suspension until the desiredamount of the at least one amphoteric and/or anionic starch is obtained.

Additionally or alternatively, the solids content of the pigmentmaterial in step c) is adjusted such that it is at least 1 wt.-%,preferably from 1 wt.-% to 80 wt.-%, more preferably from 5 wt.-% to 60wt.-%, even more preferably from 10 wt.-% to 50 wt.-% and mostpreferably from 15 wt.-% to 45 wt.-%, based on the total weight of theaqueous pigment material suspension.

Additionally or alternatively, the solids content in step c) is adjustedsuch that it is at least 1 wt.-%, preferably from 1 wt.-% to 80 wt.-%,more preferably from 5 wt.-% to 60 wt.-%, even more preferably from 10wt.-% to 50 wt.-% and most preferably from 15 wt.-% to 45 wt.-%, basedon the total weight of the aqueous pigment material suspension.

The solids content of the suspension can be adjusted by methods known tothe skilled person. To adjust the solids content of an aqueous pigmentmaterial comprising suspension, the suspension may be partially or fullydewatered by a filtration, centrifugation or thermal separation process.For example, the suspension may be partially or fully dewatered by afiltration process such as nanofiltration or a thermal separationprocess such as an evaporation process. Alternatively, water may beadded to the particulate material of the aqueous pigment materialsuspension (e.g. resulting from filtration) until the desired solidscontent is obtained. Additionally or alternatively, a self-bindingpigment particle suspension having an appropriate lower content of solidparticles may be added to the particulate material of the aqueouspigment material suspension until the desired solids content isobtained.

In the process of the present invention, the at least one amphotericand/or anionic starch can be mixed with the aqueous pigment materialsuspension by any conventional mixing means known to the skilled person.

The aqueous pigment material suspension can be mixed with the at leastone amphoteric and/or anionic starch in any appropriate form, e.g. inthe form of a starch solution or a dry material. Preferably, the atleast one amphoteric and/or anionic starch is in form of a starchsolution.

In one preferred embodiment of the present invention, the at least oneamphoteric and/or anionic starch is in form of an aqueous starchsolution or starch suspension having a starch concentration from 1 wt.-%to 30 wt.-%, preferably from 1 wt.-% to 25 wt.-%, more preferably from 1wt.-% to 20 wt.-% and most preferably from 1 wt.-% to 15 wt.-%, based onthe total weight of dry pigment material in the aqueous pigment materialsuspension.

In one preferred embodiment of the present invention, the temperaturesof the at least one amphoteric and/or anionic starch in form of a starchsolution or starch suspension and the aqueous pigment materialsuspension are of about the same temperature.

Preferably, the temperature of the starch solution or starch suspensionand the temperature of the aqueous pigment material suspension differ ofnot more than 15° C., more preferably not more than 10° C. and mostpreferably not more than 5° C.

For example, the aqueous pigment material suspension having atemperature of ≤40° C., preferably between 5° C. and 40° C., morepreferably between 10° C. and 40° C. and most preferably from 15° C. to30° C. is mixed with the at least one amphoteric and/or anionic starchin form of a starch solution or starch suspension. Preferably, thestarch solution or starch suspension mixed into the aqueous pigmentmaterial suspension has a temperature of ≤40° C., preferably between 5°C. and 40° C., more preferably between 10° C. and 40° C. and mostpreferably from 15° C. to 30° C. In one preferred embodiment of thepresent invention, the aqueous pigment material suspension having atemperature of about room temperature is mixed with the at least oneamphoteric and/or anionic starch in form of a starch solution or starchsuspension having a temperature of about room temperature.

In one preferred embodiment of the present invention, the aqueouspigment material suspension obtained in step c) has a pH from 6 to 12,preferably from 6.5 to 10 and more preferably from 7 to 9.

Step d): Combining the Aqueous Pigment Material Suspension and Starch

According to step d) of the process of the present invention, theaqueous pigment material suspension and starch comprised in the mixtureof step c) is combined by grinding.

The grinding process may be undertaken by all the techniques andgrinders well known to the man skilled in the art for wet grinding. Thegrinding step may be carried out with any conventional grinding device,for example, under conditions such that comminution predominantlyresults from impacts with a secondary body, i.e. in one or more of: aball mill, a rod mill, a vibrating mill, a centrifugal impact mill, avertical bead mill, an attrition mill, or other such equipment known tothe skilled person. The grinding step d) may be carried out in batch orcontinuously, preferably continuously.

In one preferred embodiment of the present invention, the aqueoussuspension to be ground has a pH from 6 to 12, preferably from 6.5 to 10and more preferably from 7 to 9.

Additionally or alternatively, the aqueous suspension obtained aftergrinding has a pH from 6 to 12, preferably from 6.5 to 10 and morepreferably from 7 to 9.

In one preferred embodiment of the present invention, grinding step d)is carried out at a temperature from 10° C. to 40° C., preferably from20° C. to 40° C. and most preferably from 20° C. to 30° C. Preferably,grinding step d) is carried out at about room temperature.

In one preferred embodiment of the present invention, grinding step d)is carried out during and/or after step c). For example, grinding stepd) is carried out during step c).

In one preferred embodiment of the present invention, the at least oneamphotheric and/or anionic starch is added at the beginning of grindingstep d).

In another preferred embodiment of the present invention, grinding stepd) is carried out in batch or continuously. For example, grinding stepd) is carried out continuously.

In one preferred embodiment of the present invention, grinding step d)is carried out until the fraction of self-binding pigment particleshaving a particle size of less than 1 μm is greater than 10 wt.-%,preferably greater than 30 wt.-%, more preferably greater than 50 wt.-%,and most preferably greater than 70 wt.-%, based on the total weight ofthe pigment particles, as measured with a Sedigraph 5120.

Additionally or alternatively, grinding step d) is carried out until thefraction of self-binding pigment particles having a particle size ofless than 2 μm is greater than 20 wt.-%, preferably greater than 40wt.-%, more preferably greater than 60 wt.-%, and most preferablygreater than 80 wt.-%, based on the total weight of the pigmentparticles, as measured with a Sedigraph 5120.

Additionally or alternatively, the self-binding pigment particlesobtained in step d) of the process of the present invention may have aweight median particle diameter d₅₀, measured according to thesedimentation method, in the range of from 0.05 μm to 3 μm, preferablyfrom 0.1 μm to 2 μm and most preferably from 0.2 μm to 1 μm, for examplefrom 0.3 μm to 0.8 μm. Additionally or alternatively, the self-bindingpigment particles obtained in step d) may have a d₉₈ of below 2.5 μm. Inone preferred embodiment of the present invention, the self-bindingpigment particles obtained in step d) may have a d₉₈ in the range offrom 0.3 μm to 15 μm, preferably from 0.5 μm to 5 μm and most preferablyfrom 0.7 μm to 2.5 μm.

According to one specific requirement of the present invention, grindingstep d) is carried out such that the amount of free starch in theobtained self-binding pigment particle suspension is less than 50 wt.-%,based on the total amount of starch added in step c).

The obtained self-binding pigment particle suspension may be alsoreferred to as “starch-PHCH” or “starch-PHCH suspension”.

In one preferred embodiment of the present invention, grinding step d)is carried out such that the amount of free starch in the obtainedsuspension is less than 45 wt.-%, preferably less than 40 wt.-% and mostpreferably less than 35 wt.-%, based on the total amount of starch addedin step c).

Preferably, the obtained self-binding pigment particle suspension has aBrookfield viscosity in the range of 1 to 3 500 mPas, preferably in therange of 10 to 3 000 mPas, more preferably in the range of 50 to 2 500mPas and most preferably in the range of 50 to 2 000 mPas.

Additionally or alternatively, the pigment material in the obtainedself-binding pigment particle suspension has a surface charge density inthe range of +2.5 μEq/g and −10 μEq/g, more preferably in the range of+2 μEq/g and −8 μEq/g and most preferably in the range of +0.5 μEq/g and−6 μEq/g.

In one preferred embodiment of the present invention, the self-bindingpigment particles obtained in step d) exhibit a BET specific surfacearea of from 1 m²/g to 150 m²/g, more preferably 1.5 m²/g to 25 m²/g,most preferably 2 m²/g to 15 m²/g and even more preferably 2.5 m²/g to10 m²/g, measured using nitrogen and the BET method according to ISO9277.

In one preferred embodiment of the present invention, the solids contentof the obtained self-binding pigment particle suspension in step d) isat least 1 wt.-%, preferably from 1 wt.-% to 80 wt.-%, more preferablyfrom 5 wt.-% to 60 wt.-%, even more preferably from 10 wt.-% to 50 wt.-%and most preferably from 15 wt.-% to 45 wt.-%, based on the total weightof the self-binding pigment particle suspension.

In one preferred embodiment of the present invention, the process of thepresent invention may lead directly to high solids suspension ofself-binding pigment particles, i.e. an additional concentration step isnot implemented in the process of the present invention.

If a high solids suspension of self-binding pigment particles isobtained, the solids content of the obtained suspension is at least 45wt.-% and preferably from 45 wt.-% to 80 wt.-%, based on the totalweight of the self-binding pigment particle suspension. For example, thesolids content of the obtained suspension is from 50 wt.-% to 80 wt.-%and most preferably from 55 wt.-% to 79 wt.-%, based on the total weightof the self-binding pigment particle suspension.

In one preferred embodiment of the present invention, the processfurther comprises step e) of concentrating the obtained self-bindingpigment particle suspension. In one preferred embodiment of the presentinvention, concentration step e) is carried out before or after step d).For example, concentration step e) is carried out before step d).Alternatively, concentration step e) is carried out after step d).

If step e) is implemented in the process of the present invention, thesolids content in the obtained self-binding pigment particle suspensionis adjusted such that it is at least 45 wt.-%, preferably from 45 wt.-%to 80 wt.-%, more preferably from 50 wt.-% to 80 wt.-% and mostpreferably from 55 wt.-% to 79 wt.-%, based on the total weight of theself-binding pigment particle suspension.

The solids content of the obtained self-binding pigment particlesuspension can be adjusted by concentrating methods known to the skilledperson. The concentrating of the corresponding pigment materialsuspension may be achieved by means of a thermal process, for example inan evaporator, or by means of a mechanical process, for example in afilter press such as nanofiltration, and/or centrifuge.

In one preferred embodiment of the present invention, the processcomprises step e) of concentrating the obtained pigment materialsuspension such that the solids content in the obtained suspension is atleast 55 wt.-%, more preferably at least 80 wt.-% and most preferably atleast 90 wt.-%, based on the total weight of the self-binding pigmentparticle suspension.

In one preferred embodiment of the present invention, the processcomprises step e) of concentrating the obtained self-binding pigmentparticle suspension such that a dry product is obtained.

The term “dry product” is understood to refer to pigment particleshaving a total surface moisture content of less than 0.5 wt.-%,preferably less than 0.2 wt.-% and more preferably less than 0.1 wt.-%,based on the total weight of the pigment particles.

If the inventive process further comprises step e) of concentrating theobtained self-binding pigment particle suspension such that a dryproduct or a suspension having a solids content of at least 55 wt.-%,more preferably at least 80 wt.-% and most preferably at least 90 wt.-%,based on the total weight of the self-binding pigment particlesuspension, is obtained, the dry product or the suspension may berediluted. If the dry product or the suspension is rediluted, the solidscontent in the obtained suspension is adjusted such that it is at least1 wt.-%, preferably from 1 wt.-% to 80 wt.-%, more preferably from 5wt.-% to 60 wt.-%, even more preferably from 10 wt.-% to 50 wt.-% andmost preferably from 15 wt.-% to 45 wt.-%, based on the total weight ofthe self-binding pigment particle suspension.

In one preferred embodiment of the present invention, a dispersing agentis added before or during or after process step c) and/or step d).

In one preferred embodiment of the present invention, the inventiveprocess does not involve the use or addition of a dispersing agentduring grinding.

In view of the very good results of the process for preparingself-binding pigment particle suspensions as defined above, a furtheraspect of the present invention refers to a self-binding pigmentparticle suspension which is obtainable by the process according to thepresent invention.

Such suspension contains self-binding pigment particles and an amount offree starch in the water phase of the suspension of less than 50 wt.-%,based on the total amount of starch added during the process. Forexample, the water phase of the self-binding pigment particles containsan amount of free starch of less than 45 wt.-%, more preferably lessthan 40 wt.-% and most preferably less than 35 wt.-%, based on the totalamount of starch added during the process.

According to another aspect of the present invention, a paper productcomprising self-binding pigment particles is provided, characterized inthat the pigment particles are at least partially coated with at leastone anionic and/or amphoteric starch.

It is preferred that the paper product comprising the inventiveself-binding pigment particles has a dry pick resistance of at least 0.5m/s, preferably at least 0.75 m/s and most preferably at least 1 m/s ata coating weight of 10 g/m².

The improved dry pick resistance of the products obtained from theself-binding pigment particle suspension of the present inventionindicates a very good adhesion of the at least one anionic and/oramphotheric starch to the surface of the pigment particles and allows,thus, for the use of the inventive self-binding pigment particles inseveral applications, e.g., paper, paint, plastic, concrete and/oragriculture applications. Another application is the coating of treeleaves and/or plant leaves to reduce sun light and UV exposure of theleave surface.

According to a further aspect of the present invention, the self-bindingpigment particle suspension obtainable by the inventive process is usedin paper applications such as in paper coating. In one exemplaryembodiment of the present invention, the self-binding pigment particlesuspension is used in paper coating applications as a support forrotogravure and/or offset and/or digital printing and/or flexographyand/or decoration surfaces. According to another aspect of the presentinvention, the self-binding pigment particle suspension obtainable bythe inventive process is used in paper applications such as fillermaterial. According to one exemplary embodiment of the presentinvention, the filler material is used in plastics, paint, concreteand/or agricultural applications. According to another exemplaryembodiment of the present invention, the self-binding pigment particlesuspension is used to reduce sun light and UV exposure of plant leaves.

It is to be understood that the advantageous embodiments described abovewith respect to the inventive process for making self-binding pigmentparticles also can be used for preparing or defining the inventivesuspension, paper product and its use. In other words, the preferredembodiments described above and any combinations of these embodimentscan also be applied to the inventive suspension, paper product and itsuse.

The scope and interest of the invention will be better understood basedon the following examples which are intended to illustrate certainembodiments of the invention and are non-limitative.

EXAMPLES A. Methods and Materials

In the following, materials and measurement methods implemented in theexamples are described.

BET Specific Surface Area of a Material

The BET specific surface area was measured via the BET method accordingto ISO 9277 using nitrogen, following conditioning of the sample byheating at 250° C. for a period of 30 minutes. Prior to suchmeasurements, the sample was filtered, rinsed and dried at 110° C. in anoven for at least 12 hours.

Particle Size Distribution (Mass % Particles with a Diameter<X) andWeight Median Diameter (d₅₀) of a Particulate Material

Weight median grain diameter and grain diameter mass distribution of aparticulate material were determined via the sedimentation method, i.e.an analysis of sedimentation behavior in a gravitational field. Themeasurement was made with a Sedigraph™ 5120.

The method and the instrument are known to the skilled person and arecommonly used to determine grain sizes of fillers and pigments. Themeasurement was carried out in an aqueous solution of 0.1 wt.-% Na₄P₂O₇.The samples were dispersed using a high speed stirrer and ultrasonic.

Molecular Weight (M_(w))

The average molecular weight (Mw) is measured as 100 mol-% sodium saltat pH 8 according to an aqueous Gel Permeation Chromatography (GPC)method calibrated with a series of five sodium polyacrylate standardssupplied by Polymer Standard Service with references PSS-PAA 18 K,PSS-PAA 8K, PSS-PAA 5K, PSS-PAA 4K and PSS-PAA 3K.

pH of an Aqueous Suspension

The pH of the aqueous suspension was measured using a standard pH-meterat approximately 22° C.

Solids Content of an Aqueous Suspension

The suspension solids content (also known as “dry weight”) wasdetermined using a Moisture Analyser HB-S from the companyMettler-Toledo, Switzerland, with the following settings: temperature of120° C., standard drying, 2.6 to 3.5 g of suspension.

Tablet Crushing Test

This test is a measure for the self-binding power of a pigment. It is ameasure for the force needed to crush tablets that were formed from theself-binding pigment slurries.

To demonstrate the suitability for the self-binding character of thepigmentary particles thus obtained, tablets were formulated using amembrane filtration process. In this regard, an apparatus of thehigh-pressure filter press type was used, manufactured from a hollowsteel tube. The said tube is closed at the top by a lid and contains thefiltration membrane at the bottom.

Tablets were formed by applying a constant pressure (15 bar) to 80 ml ofthe starch PHCH suspension measured for 10 to 30 min such that water isreleased by filtration through a fine 0.025 μm filter membrane resultingin a compacted tablet. This method produces tablets of about 4 cmdiameter with a thickness of 1.5 to 2.0 cm. The obtained tablets weredried in an oven at 60° C. for 24 hours.

The device and method used are described in detail in the documententitled “Modified calcium carbonate coatings with rapid absorption andextensive liquid uptake capacity” (Colloids and Surfaces A, 236 (1-3),2003, pp. 91-102).

Subsequently, the tablets were fashioned by grinding into disc-shapedsamples of 2.0-2.1 cm diameter with a thickness of 0.6-0.7 cm for thestrength test analysis by using a disk mill (Jean Wirtz, Phoenix 4000).This procedure is described in the document entitled “Fluid transportinto porous coating structures: some novel findings” (Tappi Journal, 83(5), 2000, pp. 77-78). These smaller tablet discs were crushed underpressure to test their strength property by using the penetrationapparatus Zwick/Roell Alround Z020 from the company Zwick GmbH & Co. KG,Ulm, Germany. The piston is brought down into contact with the sample ata deformation speed of 3 mm per minute, the test stops at 95%deformation or 20 kN. At the first local maximum in the measurement acrack in the sample occurred. The values given herein are the average ofthree, alternatively two to five, measurements of independently preparedtablets and the error bars are the standard deviation of these threemeasurements.

Polyelectrolyte Titration by Means of SCD

The polyelectrolyte titration was performed on the particle chargedetector (Streaming current detector) Mütek PCD-03-pH of BTG InstrumentsGmbH, Herrsching, Germany by using the Mettler T90 titrator ofMettler-Toledo GmbH, Giessen, Germany.

The following ready-made solutions were used for the polyelectrolytetitration:

Cationic reagent: 0.0025 N Poly DADMAC(Poly(diallyldimethyl-ammonium-chloride) for anionic samples availablefrom Sigma-Aldrich GmbH, Buchs, Switzerland.

Anionic reagent: 0.0025 N K-Polyvinyl-Sulfate (KPVS) for cationicsamples available from WAKO Chemicals GmbH, Neuss, Germany.

Procedure

A solution was prepared in the detector by the addition of 0.5 ml KPVS(for cationic samples) to 10 ml distilled water. Then, the titrationwith Poly DADMAC was carried out until it is back to shortly after theequivalence point.

Experience shows that between 0.5 and 2.0 ml of 0.0025 molar reagentshould be used up during the titration to obtain reproducible values.This means that in the case of KPVS (for cationic samples) with 0.0025mol/1 the consumption is between 1 and 4 ml.

Depending on the charge to be expected, the following weight-inquantities have to be chosen:

Charge Weight-in [μEq/g] [g] 0.1 30.0 1.0 3.0 10.0 0.30 100.0 0.03

Small quantities were weighed into the detector by means of a taredsingle-use syringe. In case of slurries tending to rapid sedimentationthe sample was drawn under stirring, by means of a tared syringe. Thecontent of the syringe was then rinsed into the sample vessel by meansof distilled water.

Subsequently, the detector was filled with distilled water up to thelower edge and the piston inserted carefully.

If a large volume has already been obtained due to a large weight-inquantity, it is filled up to a volume which is not exceeded in thesubsequent comparison measurements. This end volume then applies for thesubsequent measurements.

Then, the oppositely charged titration solution is added into thetitrator and the top of the burette is fixed at the detector ensuringthat it does not come into contact with the detector or the liquid.

The titrator is started according to the apparatus configuration. Inparticular, the titration is equilibrium controlled, i.e. the titratoradds, if necessary in several cycles, between 0.02 and 0.1 ml (in eachcycle) of the respective cationic or anionic titration solution to thesolution to be measured until a total signal change of about 8 mV isobtained. If the signal does not change by more than 2 mV per 2 secondsand a subsequent period of 5 to 60 seconds within each cycle, thetitrator again adds between 0.02 to 0.1 ml of the respective cationic oranionic titration solution to the solution to be measured. Theequivalence point is reached for each measurement at about 0 mV.

In case of computer-controlled titrators, the calculation of the chargeis made automatically.

After each titration, the development of the titration was verified withthe aid of the titration curve.

All values are based on the triple determination of the electrochemicalcharge.

The electrochemical charge has been determined by using the followingequations:

${{Charge}\mspace{14mu}\left\lbrack {µ\; {Eq}\text{/}g} \right\rbrack} = {{\frac{V \cdot c \cdot z \cdot t}{E \cdot F} \cdot {K\left\lbrack {{Coulomb}\text{/}g} \right\rbrack}} = {{\left\lbrack {µ\; {Eq}\text{/}g} \right\rbrack \cdot 0.096485}\mspace{14mu} {Conversion}\mspace{14mu} {by}\mspace{14mu} {the}\mspace{14mu} {Faraday}\mspace{14mu} {constant}}}$wherein: anionic:  K = −1  000${{cationic}\text{:}\mspace{14mu} K} = {{+ 1}\mspace{14mu} 000\begin{matrix}{V\text{:}\mspace{14mu} {Consumption}\mspace{14mu} {{KPVS}/{PolyDADMAC}}} & \lbrack{ml}\rbrack \\{c\text{:}\mspace{14mu} {Conventration}\mspace{14mu} {{KPVS}/{PolyDADMAC}}} & \left\lbrack {{mol}\text{/}l} \right\rbrack \\{t\text{:}\mspace{14mu} {{Titer}/{factor}}\mspace{14mu} {{KPVS}/{PolyDADMAC}}} & \; \\{E\text{:}\mspace{14mu} {Weight}\text{-}{in}\mspace{14mu} {quantity}} & \lbrack g\rbrack \\{{F\text{:}\mspace{14mu} {Mass}\mspace{14mu} {fraction}\mspace{14mu} {solids}},\left. {{i.e.\mspace{14mu} 50}\% \mspace{14mu} {solids}}\Rightarrow 0.50 \right.} & \left\lbrack {g\text{/}g} \right\rbrack \\\left. {z\text{:}\mspace{14mu} {Valence}\mspace{14mu} \left( {{equivalence}\mspace{14mu} {number}} \right)}\Rightarrow{{mostly}\mspace{14mu} 1} \right. & \;\end{matrix}}$

It should be noted that the unit “Eq” is equivalent to 1 proton, thecharge of the proton being +1 e=1.602×10⁻¹⁹ As=1.602×10⁻¹⁹ C.

Adhesion Test

The adhesion test was carried out by determining the force necessary toseparate a coating layer from a support. The ground suspensions werecoated on a plastic support (PP foils) at a range of different coatweights using a laboratory coater Typ Model 624 from the companyErichsen, Germany. Polypropylene foils (YUPO Synteap foils) used in theadhesion test were obtained from the company Fischer Papier AG,Switzerland. The thickness of the white semi-matt foils was 80 μm. Theadhesion was measured as follows:

20 mm of an adhesive-tape-strip (length around 30 mm, width 19 mm,Scotch™ magic 3M 810 produced by 3M) was stuck to the coated foil. Theprotruding end was attached to a spring balance (precision balance, type20100 by Pesola, measurement range 0 to 100 g). After gluing the coatedfoil to the ground/base table, the spring balance was pulled vertically(angle of 90°) to the ground at a speed of around 30 cm/min wherein thedeviation, i.e. the extension of the spring was measured. Adhesion ofthe coating to the PP-foil was determined by the weight required toinduce a removal/de-bonding of the coating from the PP-foil. Values ofgreater than 100 g indicate that the coating did not de-bond during themeasurement.

Brookfield Viscosity

The Brookfield viscosity of the self-binding pigment particlessuspension and coating color were measured after one hour of productionand after one minute of stirring at room temperature at 100 rpm by theuse of a Brookfield viscometer type RVDVII+equipped with an appropriatespindle.

Intrinsic Viscosity

The intrinsic viscosity was determined by a Schott AVS 370 system. Thesamples were dissolved in a 0.2 M NaCl solution, and subsequently, thepH was adjusted to 10 with NaOH. Measurements were performed at 25° C.with a capillary type 0a and corrected using the Hagenbach correction.

Dry Pick Resistance

Dry pick resistance was determined by a Multipurpose printability tester(Prüfbau Instruments) at 23° C. and a contact pressure of 150 N/cm. Thistest was carried out with increasing printing speed between 0 and 3 m/s.If no differentiation is obtained the printing is further carried out ata constant printing speed (starting at 3 m/s) with 0.5 m/s intervalsuntil a printing speed of 6 m/s is reached. Low tack, normal tack andhigh tack ink (Michael Huber, Germany) were used as colour in an amountof 200 mm³.

Brightness (R457)

Brightness was measured by using a spectrophotometer (Elrepho No. 1686,Datacolor) in accordance with DIN 53146. The term “brightness” as usedin the context of the present invention is a measurement of thepercentage of diffuse light reflected from a paper's surface. A brightersheet reflects more light. As used herein, brightness of the paper maybe measured at a mean wavelength of light of 457 nm and is specified inpercent.

Opacity

Opacity was measured by using a spectrophotometer (Elrepho No. 1686,Datacolor) in accordance with DIN 53146. The term “opacity” as used inthe context of the present invention is a measurement of the opticalcoverage of a paper. A more translucent paper is more see-through. Themeasurement is based on the relation between the reflections of a singlepaper sheet in front of a black background to a non-translucent stack ofpaper. The opacity of the paper is specified in percent. Values close to100% correspond to a high opacity.

Light Scattering Coefficient “S” and Light Absorption Coefficient “K”

The light scattering coefficient “S” and the light absorptioncoefficient “K” were measured on sheets of synthetic paper (Yuko,Synteape, Fischer Papier AG, Switzerland). These paper sheets eachhaving A4 paper size were subjected to a light radiation of wavelength457 nm on a black plate using an Elrepho™ 450X, serial no 1686spectrophotometer from Datacolor (Switzerland) to determine the degreeof brightness (R457) of the coated papers on a black background (blacktrap) and on a stack of 15 non-coated sheets of paper.

A paper coating color was prepared by mixing 4 parts (on dry basis) ofAcronal™ S 360 D, BASF, a paper coating styrene acrylic latex binder (8parts of starch PHCH) and 100 parts (on dry basis) of the calciumcarbonate suspension (which is a HCB95 slurry at s.c. 78%).Alternatively, the starch PHCH was used directly as a paper coatingcolor. The coating color is then applied on the pre-weighed paper sheetsin different coating weights ranging from 4 g/m² and 56 g/m² by usingthe rod bench top coater, Rakelauftragsgerät K-Control-Coater K202,Model 624 from Erichsen, Hemer, Germany.

Subsequently, the coated paper sheets were dried until a constant weightwas reached, e.g. by drying the paper sheets at 150° C. on a belt dryerat a speed of 7.0 m/min.

The coated paper sheets with different coating weights of between 4 g/m²and 56 g/m² and samples of uncoated paper were then subjected to lightradiation of wavelength 457 nm using an Elrepho™ 450X, serial n° 1686spectrophotometer from Datacolor (Switzerland) on a black plate todetermine the degree of whiteness (R457) of the paper on a blackbackground (black trap) and on a pile of 15 non-coated sheets of paper.Subsequently, the coated paper sheets were cut into sheets each havingdimensions of 16 cm*18 cm and weighed. The light scattering coefficient“S” and the light absorption coefficient “K” were then calculated inaccordance with the Kubelka-Munk theory, which is well-known to experts,and described in the publications of Kubelka and Munk (Zeitschrift fürTechnische Physik 12, 539, (1931)), and of Kubelka (J. Optical Soc. Am.38(5), 448, (1948) and J. Optical Soc. Am. 44(4), 330, (1954)). Thelight scattering coefficient “S” and the light absorption coefficient“K” are quoted as the value interpolated at the coat weight 20 g/m².

Glossiness (75° Tappi (ISO 8254-1)

The 75° glossiness of the sheet of paper previously coated wasdetermined by the TAPPI method in accordance with ISO 8254-1 by using aLehmann™ laboratory glossmeter (Lehmann LGDL-05.3) before as well asafter calendering. As used herein, glossiness of the paper is specifiedin percent.

Chemical Oxygen Demand

Chemical oxygen demand (COD) was measured according to the Lange Method(ISO 15705), as described in the document issued by HACH LANGE LTD,entitled “DOC042.52.20023.Nov08”. Approximately, 100 ml of the liquidphase were added in a Lange CSB LCK 014 cuvette, covering a rangebetween 1 000 and 10.000 mg/l and heated in the closed cuvette for twohours at 148° C. in a dry thermostat. This suspension was then analyzedaccording to the Lange Method.

Thermo Gravimetric Analysis

Thermo gravimetric analysis (TGA) was performed on the Mettler ToledoTGA/STDA 851^(e) at 570° C. for 1 h in air (PPH Methode Q60B Hybrid,570° C./1 h air).

Degree of Carboxylation

Degree of carboxylation was measured by a conductometric titration. Thestarch was added portion wise under stirring into water and stirred witha magnetic bar until a clear solution was obtained. The solution had astarch concentration of 3 wt.-%, based on the total weight of thesolution. The solutions were shaked before use. The pH of the solutionwas adjusted to 3 by using aqueous HCl at 6% concentration. The solutionwas then titrated with 0.1 M aqueous NaOH and the pH and conductivitywere measured.

At the beginning of titration, the conductivity decreased until itreached a minimum. The slope was negative and corresponds to thetitration of excess HCl. Then the conductivity increased again with aweak slope which corresponds to the deprotonation of the anionic groupsof the starch. At the end, the slope of conductivity increased morewhich corresponds to the excess of NaOH.

The measurement was repeated three times for each sample.

d/d

The term “d/d” refers to the dry amount based on the dry amount ofpigment material.

B. Preparation and Testing of Self-Binding Pigment Particle Suspensionsand Corresponding Coatings Example 1 (Comparative Example) a)Preparation and Testing of the Self-Binding Pigment Particle Suspension

A self-binding pigment particle suspension was prepared by usingundispersed calcium carbonate ground with cationic starch.

A starch solution having a starch concentration of 20 wt.-%, based onthe total weight of the solution, was prepared by stirring 13 wt.-% (d/dwhich corresponds to 15 pph starch on 100 pph calcium carbonate), basedon the total weight of the dry pigment material in the calcium carbonateslurry and starch, of a commercially available cationic starch (C*film05978, from Cargill) in water at a temperature of about 95° C.

10 kg of undispersed calcium carbonate slurry was prepared having asolids content of about 20 wt.-%, based on the total weight of theslurry. The particulate material of the slurry has a weight medianparticle diameter d₅₀ value of 0.7 μm (measured according to thesedimentation method). Furthermore, the particulate material (calciumcarbonate) of the slurry had a specific surface area of 9.5 m²/g(measured using nitrogen and the BET method).

Subsequently, the calcium carbonate slurry was run through a DynomillMultilab filled with 1 070 g (with 80% filler level) zirconiumoxide/zirconium silicate grinding beads (0.6-1.0 mm) at about roomtemperature. The grinding chamber had a total volume of 600 cm³. Themill speed was set to 2 500 rpm and the flow was set to 500 cm³/min.

Within 9 min, starting at grinding start, the starch solution wasblended through a peristaltic pump over a three way valve directly intothe inlet of the Dynomill Multilab mill to 100 pph (d/d), based on thetotal weight of dry calcium carbonate in the slurry, of the calciumcarbonate slurry at room temperature.

The calcium carbonate slurry was ground together with the starchsolution to a target particle size of 98 wt.-% less than 2 μm and 80wt.-% less than 1 μm, measured on a Sedigraph 5120. At the end of thegrinding process, 4.99 ml (750 ppm based on the amount of water in theslurry) of a commercially available preserving agent (OmyAK, Rohm andHaas, Frankfurt, Germany) was added to the self-binding pigment particlesuspension (starch PHCH-1 suspension) in circulation and stirred for 5min. The obtained starch PHCH-1 suspension had a solids content of 20.9wt.-%, based on the total weight of the suspension.

The polyelectrolyte titration of the starch PHCH-1 suspension gave acharge density of +4.5 μEq/g.

The details regarding the starch solution, calcium carbonate slurry andstarch PHCH-1 suspension before up concentration as well as the trialconditions are summarized in Table 1.

TABLE 1 Self-binding pigment Starch solution CaCO₃ slurry particlesuspension (cationic) (undispersed) (Starch PHCH-1) pph s.c. T pph s.c.T s.c. Target PSD of (d/d) [wt.-%] [° C.] (d/d) [wt.-%] [° C.] [wt.-%]grinding 15 20 95 100 20 RT 20.9 98 wt.-% < 2 μm s.c. = solids content;RT = room temperature

Subsequently, the starch PHCH-1 suspension was concentrated bycentrifugation (Centrifuge Rotina 420, Hettich Laborapparate) at 3 000rpm for about 15 min. The obtained filter cake had solids content of58.5 wt.-%, based on the total weight of the filter cake, and wasrediluted to final solids content of about 44.2 wt.-%, based on thetotal weight of the filter cake.

The starch PHCH suspension as well as the filter cake comprising theself-binding pigment particles (starch PHCH-1) was, after drying,analyzed by thermogravimetric analysis (TGA). The TGA analysis for thestarch PHCH suspension provided an amount of starch of 12.87 wt.-%,based on the total weight of the suspension. The TGA analysis for thefilter cake provided an amount of starch of 4.84 wt.-%, based on thetotal weight of the filter cake.

From the measured details, it can be gathered that the amount ofcationic starch found in the starch PHCH suspension (˜12.87 wt.-%)corresponds widely to the amount of cationic starch blended into thecalcium carbonate slurry during grinding (˜13 wt.-%). However, from theamount of starch found in the filter cake (˜4.84 wt.-%) it can befurther concluded that approximately 8 wt.-% of the cationic starchblended into the calcium carbonate slurry during grinding must have goneinto the water phase. Thus, it has to be assumed that the preparation ofthe starch PHCH suspension by grinding of calcium carbonate slurry withcationic starch results in a suspension in which about 62 wt.-%, basedon the total weight of starch, is present in the form of free starch.

b) Preparation and Testing of Coating Colors Prepared from theSelf-Binding Pigment Particle Suspension

Two coating colors were prepared by using the starch PHCH-1 suspension(cationic) in the form of a filter cake having a solids content of 44.2wt.-%, based on the total weight of the filter cake.

Coating Color-1 (Cationic)

100 pph of the starch PHCH-1 suspension (cationic) in the form of afilter cake having solids content of 44.2 wt.-% was used as pure coatingcolor. Coating color-1 provided a Brookfield viscosity of 207 mPas.

The S-coefficient of coating color-1 was determined as being 210 m²/kg,while the K-coefficient was determined as being 0.271 m²/kg.

Coating color-1 was applied on two different base papers, Synteape,commercially available from Fischer Papier AG, Switzerland as well asSAPPI, commercially available from Sappi Magnostar GmbH, Austria. Thebase paper from Sappi Magnostar corresponds to an uncoated raw paper.Furthermore, each base paper was provided as calendered and uncalenderedsamples. The coatings have been applied with a rod bench top coater,Rakelauftragsgerät K-Control-Coater K202, Model 624 (Erichsen)/Fabr. No.57097-4/Rods 1-5 for the control of the liquid flow/Belt dryer 7.0mmin⁻¹, 150° C.

Mechanical properties of the uncalendered samples were characterized bythe dry pick resistance test which was carried out with coating weightsbetween 5 g/m² and 31 g/m². The dry pick resistance test provided a pickvelocity of below 0.5 m/s across all coat weights of both of theuncalendered paper samples.

The optical properties of the uncalendered paper samples werecharacterized by brightness, opacity and paper gloss for coating weightsbetween 5 g/m² and 30 g/m². In addition thereto, the calendered papersamples were characterized by the paper gloss for coating weightsbetween 5 g/m² and 30 g/m².

The results for the mechanical and optical properties of the testedpapers can be gathered from Tables 2 to 4.

TABLE 2 Dry pick resistance Synteape Coat Pick Sappi base paper Coatingweight velocity Coat weight Pick velocity color [gm⁻²] [ms⁻¹] [gm⁻²][ms⁻¹] 1 5.2 <0.5 13.1 <0.5 15.2 <0.5 20.1 <0.5 30.2 <0.5 — —

Mechanical properties, like dry pick resistance, and the coat weightscorrespond to rods 1, 3 and 5

TABLE 3 Optical properties Synteape Coat Brightness Paper gloss 75°Coating weight R-457 Opacity Tappi [%] color [gm⁻²] [%] [%] uncalenderedcalendered 1 5.2 91.1 93.7 26.6 69.1 8.8 91.1 94.3 26.6 69.4 15.2 91.595.7 27.2 69.6 23.8 91.7 96.9 26.7 68.7 30.2 91.9 97.5 25.9 68.4

The coat weights correspond to rods 1, 3, 4, 5

TABLE 4 Optical properties Sappi base paper Coat Brightness Paper gloss75° Coating weight R-457 Opacity Tappi [%] color [gm⁻²] [%] [%]uncalendered calendered 1 13.1 86.7 93.6 10.7 60.4 15.1 87.0 94.4 12.260.6 20.1 88.1 96.0 15.1 64.4

The coat weights correspond to rods 1, 2, 3, 4, 5

Coating Color-2 (Cationic)

Coating color-2 having a solids content of 60.1 wt.-%, based on thetotal weight of the coating color, was prepared by adding 8 pph (d/d) ofthe starch PHCH-1 suspension (cationic) in form of a filter cake havinga solids content of 44.2 wt.-% to 100 pph (d/d) of a calcium carbonateslurry having solids content of 78 wt.-%, based on the total weight ofthe slurry. The particulate material of the calcium carbonate slurry hasbeen wet ground in the presence of a sodium polyacrylate and has aweight median particle diameter d₅₀ value of 0.65 μm and a d₉₅ of lessthan 2 μm (all measured according to the sedimentation method) and aspecific surface area of 14.8 m²/g (measured using nitrogen and the BETmethod). Furthermore, 4 pph (d/d) of commercially availablestyrene/acrylate basic latex as e.g. sold by the BASF Company under thename ACRONAL S 360 D™ was added. Coating color-2 provided a Brookfieldviscosity of 96 mPas.

The S-coefficient of coating color-2 was determined as being 99 m²/kgwhile the K-coefficient was determined as being −0.09 m²/kg.

Coating color-2 was also applied on two different base papers, namelySynteape, commercially available from Fischer Papier AG, Switzerland aswell as SAPPI, commercially available from Sappi Magnostar GmbH,Austria. The base paper from Sappi Magnostar corresponds to an uncoatedraw paper. Furthermore, each base paper was provided as calendered anduncalendered sample. The coatings have been applied with a rod bench topcoater, Rakelauftragsgerät K-Control-Coater K202, Model 624(Erichsen)/Fabr. No. 57097-4/Rods 1-5 for the control of the liquidflow/Belt dryer 7.0 m/min, 150° C.

Mechanical properties of the uncalendered samples were characterized bythe dry pick resistance test which was carried out with coating weightsbetween 8 g/m² and 56 g/m². The dry pick resistance test provided a pickvelocity of below 1 m/s across all coat weights of both of theuncalendered paper samples. In particular, on Synteape a pick velocityof 1.0 m/s was determined for a 8.1 g/m² coating weight, while at 22.7g/m² coating weight the pick velocity was at 0.5 m/s and at 47.6 g/m²coating weight the pick velocity was below 0.5 m/s. In contrast thereto,on SAPPI, a pick velocity of below 0.5 m/s was determined for allcoatings weights beginning at a coating weight of 16.3 g/m².

The optical properties of the uncalendered paper samples werecharacterized by brightness, opacity and paper gloss for coating weightsbetween about 8 g/m² and 56 g/m². In addition thereto, the calenderedpaper samples were characterized by the paper gloss for coating weightsbetween about 8 g/m² and 56 g/m².

The results for the mechanical and optical properties of the testedpapers can be gathered from Table 5 to 7.

TABLE 5 Dry pick resistance Synteape Coat Pick Sappi base paper Coatingweight velocity Coat weight Pick velocity color [gm⁻²] [ms⁻¹] [gm⁻²][ms⁻¹] 2 8.1 1.0 16.3 <0.5 22.7 0.5 29.1 <0.5 47.6 <0.5 55.8 <0.5

Mechanical properties, like dry pick resistance, and the coat weightscorrespond to rods 1, 3 and 5

TABLE 6 Optical properties Synteape Coat Brightness Paper gloss 75°Coating weight R-457 Opacity Tappi [%] color [gm⁻²] [%] [%] uncalenderedcalendered 2 8.1 90.9 93.2 60.3 79.2 13.1 90.9 93.6 64.0 79.9 22.7 91.094.3 66.7 80.1 36.3 91.2 96.1 68.9 80.5 47.6 91.2 96.7 70.7 80.7

The coat weights correspond to rods 1, 3, 4, 5

TABLE 7 Optical properties Sappi base paper Coat Brightness Paper gloss75° Coating weight R-457 Opacity Tappi [%] color [gm⁻²] [%] [%]uncalendered calendered 2 16.3 86.2 92.2 21.3 66.8 20.1 86.6 93.0 24.272.3 29.7 87.4 94.8 29.3 74.9 42.7 88.7 95.5 34.8 76.3 55.8 88.7 97.034.7 76.3

The coat weights correspond to rods 1, 2, 3, 4, 5

Example 2 (Inventive Example) a) Preparation and Testing of theSelf-Binding Pigment Particle Suspension

A self-binding pigment particle suspension was prepared by usingundispersed calcium carbonate ground with a thermally modified starch inan amount of about 0.99 wt.-% (corresponds to 1 pph starch on 100 pphcalcium carbonate) and about 4.76 wt.-% (corresponds to 5 pph starch on100 pph calcium carbonate), respectively.

A starch suspension having a starch concentration of 40 wt.-%, based onthe total weight of the suspension, was prepared by stirring 0.99 wt.-%(d/d which corresponds to 1 pph starch on 100 pph calcium carbonate),based on the total weight of the dry pigment material in the calciumcarbonate slurry and starch, of a commercially available thermallymodified starch (C*film 07311, from Cargill) in water at roomtemperature.

Furthermore, a starch suspension having a starch concentration of 40wt.-%, based on the total weight of the suspension, was prepared bystirring 4.76 wt.-% (d/d; corresponds to 5 pph starch on 100 pph calciumcarbonate), based on the total weight of the dry pigment material in thecalcium carbonate slurry and starch, of a commercially availablethermally modified starch (C*film 07311, from Cargill) in water at roomtemperature.

10 kg of undispersed calcium carbonate slurry was prepared having solidscontent of about 20 wt.-%, based on the total weight of the slurry. Theparticulate material of the slurry has a weight median particle diameterd₅₀ value of 0.74 μm (measured according to the sedimentation method).

Furthermore, the particulate material of the slurry had a specificsurface area of 9.46 m²/g (measured using nitrogen and the BET method).

Subsequently, the calcium carbonate slurry was run through a DynomillMultilab filled with 1 070 g of (with 80% filler level) zirconiumoxide/zirconium silicate grinding beads (0.6-1.0 mm) at about roomtemperature. The grinding chamber had a total volume of 600 cm³. Themill speed was set to 2 500 rpm and the flow was set to 500 cm³/min.

Within 5 and 10 min, respectively, starting at grinding start, each ofthe starch suspensions were blended through a peristaltic pump over athree way valve directly into the inlet of the Dynomill Multilab mill to100 pph (d/d) of calcium carbonate slurry, based on the dry weight ofthe calcium carbonate in the slurry.

The obtained calcium carbonate slurries were ground together with therespective starch suspension to a target particle size of 98 wt.-% lessthan 2 μm and approx. 80 wt.-% of less than 1 μm, measured on aSedigraph 5120. At the end of the grinding process, 5.3 ml (750 ppmbased on the total amount of water amount) of a commercially availablepreserving agent (OmyAK, Rohm and Haas) was added to each of theself-binding pigment particle suspensions (starch PHCH suspensions) incirculation and stirred for 5 min. The obtained starch PHCH suspensionprepared by adding about 0.99 wt.-% of the thermally modified starch hada solid content of 40 wt.-%, based on the total weight of thesuspension, (starch PHCH-2) comprising particles having a charge densityof +1.63 μEq/g while the obtained starch PHCH suspension prepared byadding about 4.76 wt.-% of the thermally modified starch had a solidcontent of 40 wt.-%, based on the total weight of the suspension,(starch PHCH-3) comprising particles having a charge density of −0.87μEq/g.

The details regarding starch suspensions, calcium carbonate slurries andstarch PHCH suspensions as well as the trial conditions are summarizedin Table 8.

TABLE 8 Self-binding pigment Starch suspension CaCO₃ slurry particlesuspension (anionic) (undispersed) (Starch PHCH) pph s.c. T pph s.c. TTarget PSD Trial (d/d) [wt.-%] [° C.] (d/d) [wt.-%] [° C.] of grindingStarch 1 40 RT 100 20 RT 98 wt.-% < 2 PHCH-2 μm Starch 5 40 RT 100 20 RT98 wt.-% < 2 PHCH-3 μm s.c. = solids content; RT = room temperature

Subsequently, both starch PHCH (starch PHCH-2 and starch PHCH-3)suspensions were concentrated by centrifugation (Centrifuge Rotina 420,Hettich Laborapparate) at 3 000 rpm for about 15 min. The filter cakeobtained from the starch PHCH-2 suspension had solids content of 59.3wt.-%, based on the total weight of the filter cake, and was redilutedto final solids content of about 43 wt.-%, based on the total weight ofthe filter cake (starch PHCH-2). The filter cake obtained from thestarch PHCH-3 suspension had solids content of 58 wt.-%, based on thetotal weight of the filter cake, and was diluted to final solids contentof about 41.8 wt.-%, based on the total weight of the filter cake(starch PHCH-3). Furthermore, the supernatant of the starch PHCH-2suspension had a pH of 8.17, while the supernatant of the starch PHCH-3suspension had a pH of 7.95.

b) Preparation of Coating Colors Prepared from the Self-Binding PigmentParticle Suspension and Adhesion Tests

The filter cakes starch PHCH-2 (coating color-3) and starch PHCH-3(coating color-4) were used directly as coating colors without addingfurther additives. As reference a coating color having solids content of33.2 wt.-%, based on the total weight of the coating color, was used.The reference coating color was prepared by diluting a calcium carbonateslurry having solids content of 67 wt.-%, based on the total weight ofthe slurry. The particulate material of this slurry had a weight medianparticle diameter d₅₀ value of 0.74 μm (measured according to thesedimentation method). Furthermore, the particulate material of theslurry had a specific surface area of 9.46 m²/g (measured using nitrogenand the BET method).

The coating weights for the reference and the inventive starch PHCHsamples used for the adhesion test as well as the test results aresummarized in Table 9.

TABLE 9 Coating weight [g/m²] Adhesion g (n = 5) Trial rod 1 rod 3 rod 5rod 1 rod 3 rod 5 Reference 3.5 10.7 22.1 0 0 0 Coating color-3 4.7 14.831.5 10.8 11.4 7.8 Coating color-4 4.8 14.2 30.0 76.0 69.0 39.0 n =number of repeat experiments/measurements

As can be gathered from the measured details, the coatings did notrelease or rip off the foil (de-bond). In particular, it can be gatheredthat a coating color prepared by using a calcium carbonate without ananionic and/or amphotheric starch shows no adhesion at all resultingthus in no binding power.

In contrast thereto, the coating color-3 comprising the inventivecomposition starch PHCH-2 (about 0.99 wt.-% or 1 pph starch) shows somebinding power. Furthermore, the coating color-4 comprising the inventivecomposition starch PHCH-3 (about 4.76 wt.-% or 5 pph starch) shows aclear increase in binding power. This test is the result of the averageof five measurements.

Example 3 (Inventive Example)

Self-binding pigment particle suspensions were prepared by usingundispersed calcium carbonate ground with a thermally modified starch atdifferent temperatures.

A starch suspension having a starch concentration of 40 wt.-%, based onthe total weight of the suspension, was prepared by stirring 13 wt.-%(d/d which corresponds to 15 pph starch on 100 pph calcium carbonate),based on the total weight of the dry pigment material in the calciumcarbonate slurry and starch, of a commercially available thermallymodified starch (C*film 07311, from Cargill) in water at roomtemperature.

10 kg of undispersed calcium carbonate slurry was prepared having solidscontent of about 20 wt.-%, based on the total weight of the calciumcarbonate slurry, at about 20° C. The particulate material of the slurryhad a weight median particle diameter d₅₀ value of 0.74 μm (measuredaccording to the sedimentation method). Furthermore, the particulatematerial of the slurry had a specific surface area of 9.46 m²/g(measured using nitrogen and the BET method).

Subsequently, the calcium carbonate slurry was run through a DynomillMultilab filled with 1 070 g (with 80% filler level) zirconiumoxide/zirconium silicate grinding beads (0.6-1.0 mm) at about roomtemperature.

The grinding chamber had a total volume of 600 cm³. The mill speed wasset to 2 500 rpm and the flow was set to 500 cm³/min.

Within 10 min, starting at grinding start, the starch suspension wasblended through a peristaltic pump over a three way valve directly intothe inlet of the Dynomill Multilab mill to 100 pph (d/d) of the calciumcarbonate slurry at a temperature of 20° C.

The calcium carbonate slurry was ground with the starch suspension to atarget particle size of 98 wt.-% less than 2 μm and 80 wt.-% less than 1μm, measured on a Sedigraph 5120. At the end of the grinding process,750 ppm based on the amount of water (4.99 ml) of a commerciallyavailable preserving agent (OmyAK, Rohm and Haas) was added to theself-binding pigment particle suspension (starch PHCH suspension) incirculation and stirred for 5 min. The starch PHCH suspension obtainedat 20° C. had solids content of 21.7 wt.-%, based on the total weight ofthe suspension (starch PHCH-4).

The details regarding the starch suspension, calcium carbonate slurryand starch PHCH suspension as well as the trial conditions aresummarized in Table 10.

TABLE 10 Self-binding pigment Starch suspension CaCO₃ slurry particlesuspension (anionic) (undispersed) (Starch PHCH) pph s.c. T pph s.c. TTarget PSD Trial (d/d) [wt.-%] [° C.] (d/d) [wt.-%] [° C.] of grindingStarch 15 40 RT 100 20 20 98 wt.-% < 2 PHCH-4 μm s.c. = solids content;RT = room temperature

Subsequently, the starch PHCH suspension was concentrated bycentrifugation (Centrifuge Rotina 420, Hettich Laborapparate) at 3 000rpm for about 15 min to solids content of 58.2 wt.-% (at 20° C.), basedon the total weight of the filter cake. The filter cake obtained wasdiluted to final solids content of about 39 wt.-%, based on the totalweight of the filter cake.

The obtained filter cake comprising the self-binding pigment particle(starch PHCH) was, after drying, analyzed by TGA and BET. The obtainedsupernatant was analyzed by COD and starch content.

Table 11 summarizes the measured details of the respective supernatantas well as the filter cake.

TABLE 11 Supernatant Filter cake (dried) Starch content TGA* BET Trial[mg/l] [wt.-%] [m²/g] Starch PHCH-4 5.559 8.2611 6.4 *The results aregiven for thermogravimetric analysis (TGA) 0-570° C. In this regard, itshould be noted that the moisture in these results is included.According to the TGA, the following data are obtained: Starch PHCH-40-180° C. 0.6416% (which is considered moisture) 180°-570° C. 7.6226%(which is considered starch, organics)

The amount of 7.6226 wt.-% starch in the filtercake corresponds to anamount of 58.6 wt.-% of the total amount of starch in the filtercake,based on the total amount of starch in the starch PHCH suspension, andtherefore 41.4 wt.-% of starch is present as free starch (through lossduring concentration as well as through microbial starch degradation).

Tablets were prepared from the self-binding pigment particle suspensionand measured in the tablet crushing test with respect to the maximumforce, F_(max), required to make the first crack into a tablet. Inparticular, tablets were prepared from starch PHCH-4 obtained in thisexample. In particular, the tablets were formed by applying a constantpressure of 15 bar to the suspension for 30 min.

The effects of the self-binding pigment particle suspension on themaximum force, F_(max), required to make the first crack into a tabletas measured in the tablet crushing test are outlined in Table 12.

TABLE 12 F_(max) Trial [N] Starch PHCH-4 507.4

The result corresponds to an average of 5 measurements.

From Table 12 it can be concluded that tablets prepared from asuspension made in accordance with the inventive process require amaximum force of about 507 N to make the first crack.

Example 4 (Inventive Example)

Self-binding pigment particle suspensions were prepared by usingundispersed calcium carbonate ground with a thermally modified starch oran anionic starch having a degree of carboxylation of about 0.0082 atdifferent temperatures.

A starch suspension-1 having a starch concentration of 40 wt.-%, basedon the total weight of the suspension, was prepared by stirring 13 wt.-%(d/d which corresponds to 15 pph starch on 100 pph calcium carbonate),based on the total weight of the dry pigment material in the calciumcarbonate slurry and starch, of a commercially available thermallymodified starch (C*film 07311, from Cargill) in water at roomtemperature.

A starch solution-2 having a starch concentration of 10 wt.-%, based onthe total weight of the solution, was prepared by stirring 13 wt.-% (d/dwhich corresponds to 15 pph starch on 100 pph calcium carbonate), basedon the total weight of the dry pigment material in the calcium carbonateslurry and starch, of a commercially available anionic starch having adegree of carboxylation of about 0.0082 (C*iCoat 07525, from Cargill) inwater at room temperature. C*iCoat 07525 is a cold water soluble starchand thus dissolves at room temperature.

10 kg of undispersed calcium carbonate slurry was prepared having asolids content of about 20 wt.-%, based on the total weight of theslurry. The particulate material of the slurries had a weight medianparticle diameter d₅₀ value of 0.74 μm (measured according to thesedimentation method). Furthermore, the particulate material of theslurries had a specific surface area of 9.46 m²/g (measured usingnitrogen and the BET method).

Subsequently, the calcium carbonate slurry was run through a DynomillMultilab filled with 1 070 g (with 80% filler level) zirconiumoxide/zirconium silicate grinding beads (0.6-1.0 mm) at about roomtemperature. The grinding chamber had a total volume of 600 cm³. Themill speed was set to 2 500 rpm and the flow was set to 500 cm³/min.

Within 10 to 15 min (15 minutes for suspension-1, 10 minutes forsolution-2), starting at grinding start, the respective starchsuspension/solution was blended through a peristaltic pump over a threeway valve directly into the inlet of the Dynomill Multilab mill to 100pph (d/d), based on the total weight of dry calcium carbonate in theslurry, of the calcium carbonate slurry at room temperature.

The respective calcium carbonate slurries were ground with therespective starch suspensions/solution to a target particle size of 98wt.-% less than 2 μm and 80 wt.-% less than 1 μm, measured on aSedigraph 5120. At the end of the grinding process, 750 ppm based on theamount of water in the starch PHCH suspension (4.8 ml for suspension-1,5.3 ml for solution-2) of a commercially available preserving agent(OmyAK, Rohm and Haas) was added to each self-binding pigment particlesuspension in circulation and stirred for 5 min.

The obtained starch PHCH suspension prepared by using starchsuspension-1 had a solids content of 20.9 wt.-%, based on the totalweight of the suspension, (starch PHCH-5) while the obtained starch PHCHsuspension prepared by using starch solution-2 had a solids content of21.2 wt.-%, based on the total weight of the suspension, (starchPHCH-6).

The details regarding starch suspension/solutions, calcium carbonateslurries and starch PHCH suspensions as well as the trial conditions aresummarized in Table 13.

TABLE 13 Self-binding Starch pigment suspension/solution CaCO₃ slurryparticle suspension (anionic) (undispersed) (Starch PHCH) pph s.c. T pphs.c. T Target PSD Trial (d/d) [wt.-%] [° C.] (d/d) [wt.-%] [° C.] ofgrinding Starch 15 40 RT 100 20 RT 98 wt.-% < 2 PHCH-5 μm Starch 15 10RT 100 20 RT 98 wt.-% < 2 PHCH-6 μm s.c. = solids content; RT = roomtemperature

Subsequently, all slurries were centrifuged (Centrifuge Rotina 420,Hettich Laborapparate) at 3 000 rpm for about 15 min. The obtainedfilter cakes were rediluted to final solids content of about 39.6 wt.-%(starch PHCH-5), based on the total weight of the filter cake and 44.5wt.-% (starch PHCH-6), respectively.

The obtained filter cakes comprising the self-binding pigment particles(starch PHCH) were, after drying, analyzed by TGA at 0 to 570° C. (notstepwise). The filter cake of starch PHCH-5 comprises an amount of 7.82wt.-% (including moisture) starch, corresponding to an amount of 60.15wt.-% of the total amount of starch in the filtercake, i.e. an amount offree starch of 39.85 wt.-%.

b) Preparation and Testing of Coating Colors Prepared from theSelf-Binding Pigment Particle Suspensions Coating colors were preparedby using the starch PHCH suspensions of this Example in the form of therespective filter cake.

Coating Color-5

100 pph of the starch PHCH-5 suspension in the form of a filter cakehaving solids content of about 39.6 wt.-% was used as pure coatingcolor. The S-coefficient of coating color-5 was determined as being 209m²/kg, while the K-coefficient was determined as being 0.235 m²/kg.

Coating Color-6

100 pph of the starch PHCH-6 suspension in the form of a filter cakehaving solids content of about 44.5 wt.-% was used as pure coatingcolor. Coating color-6 provided a Brookfield viscosity of 90 mPas. TheS-coefficient of coating color-6 was determined as being 205 m²/kg,while the K-coefficient was determined as being 0.406 m²/kg.

Coating colors-5 and 6 were applied on two different base papers,Synteape, commercially available from Fischer Papier AG, Switzerland aswell as SAPPI, commercially available from Sappi Magnostar GmbH,Austria. The base paper from Sappi Magnostar corresponds to an uncoatedraw paper. Furthermore, each base paper was provided as calendered anduncalendered sample. The coatings have been applied with a rod bench topcoater, Rakelauftragsgerät K-Control-Coater K202, Model 624(Erichsen)/Fabr. No. 57097-4/Rods 1-5 for the control of the liquidflow/Belt dryer 7.0 m/min, 150° C.

Mechanical properties of the uncalendered samples were characterized bythe dry pick resistance test which was carried out with coating weightsbetween 4 g/m² and 30.48 g/m². The results for the dry pick resistancetest of the tested papers can be gathered from Table 14.

The optical properties of the uncalendered paper samples werecharacterized by brightness, opacity and paper gloss for coating weightsbetween about 4 g/m² and 30.5 g/m². In addition thereto, the calenderedpaper samples were characterized by the paper gloss for coating weightsbetween about 4 g/m² and 30.5 g/m². The results for the opticalproperties of the tested papers can be gathered from Tables 15 to 17.

TABLE 15 Dry pick resistance Synteape Coat Pick Sappi base paper Coatingweight velocity Coat weight Pick velocity color [gm⁻²] [ms⁻¹] [gm⁻²][ms⁻¹] 5 4.0 <0.5 12.3 <0.5 12.7 <0.5 — — 26.3 <0.5 — — 6 5.1 0.9 11.7<0.5 15.1 <0.5 15.7 <0.5 29.1 <0.5 — —

Mechanical properties, like dry pick resistance, and the coat weightscorrespond to rods 1, 3 and 5

TABLE 16 Optical properties Synteape Coat Brightness Paper gloss 75°Coating weight R-457 Opacity Tappi [%] color [gm⁻²] [%] [%] uncalenderedcalendered 5 4.0 90.9 93.4 10.6 81.3 7.5 91.1 94.2 11.8 85.8 12.7 91.595.3 10.8 84.2 21.2 91.8 96.3 7.0 71.7 26.3 91.9 97.1 7.0 75.1 6 5.190.7 93.8 33.0 81.4 7.5 90.8 94.4 22.8 78.9 15.1 90.8 95.6 12.2 72.923.1 90.9 97.0 16.6 78.8 29.1 90.9 97.8 19.4 75.7

The coat weights correspond to rods 1, 2, 3, 4, 5

TABLE 17 Optical properties Sappi base paper Coat Brightness Paper gloss75° Coating weight R-457 Opacity Tappi [%] color [gm⁻²] [%] [%]uncalendered calendered 5 12.3 87.2 92.7 6.3 67.9 13.1 87.8 93.4 6.268.4 6 11.7 86.9 93.3 47.9 62.1 15.7 87.2 94.0 42.8 65.4 20.5 87.2 96.333.5 67.2

The coat weights correspond to rods 1, 2, 3, 4, 5

Coating Color-7

Coating color-7 having a solids content of 59.7 wt.-%, based on thetotal weight of the coating color, was prepared by adding 8 pph (d/d) ofthe starch PHCH-5 suspension in form of a filter cake having a solidscontent of 39.6 wt.-% to 100 pph (d/d) of a calcium carbonate slurryhaving solids content of 78 wt.-%, based on the total weight of theslurry. The particulate material of the calcium carbonate slurry hasbeen wet ground in the presence of a sodium polyacrylate and has aweight median particle diameter d₅₀ value of 0.65 μm and a d₉₅ of lessthan 2 μm (all measured according to the sedimentation method) and aspecific surface area of 14.8 m²/g (measured using nitrogen and the BETmethod). Furthermore, 4 pph (d/d) of commercially availablestyrene/acrylate basic latex as e.g. sold by the BASF Company under thename ACRONAL S 360 D™ was added.

The S-coefficient of coating color-8 was determined as being 113 m²/kgwhile the K-coefficient was determined as being 0.064 m²/kg.

Coating Color-8

Coating color-8 having a solids content of 59.5 wt.-%, based on thetotal weight of the coating color, was prepared as described for coatingcolor 7, except that the starch PHCH-6 suspension in form of a filtercake having a solids content of 44.5 wt.-% was used. Coating color-8provided a Brookfield viscosity of 59 mPas. The S-coefficient of coatingcolor-8 was determined as being 106 m²/kg while the K-coefficient wasdetermined as being −0.345 m²/kg.

Coating colors-7 and 8 were also applied on two different base papers,namely Synteape, commercially available from Fischer Papier AG,Switzerland as well as SAPPI, commercially available from SappiMagnostar GmbH, Austria. The base paper from Sappi Magnostar correspondsto an uncoated raw paper. Furthermore, each base paper was provided ascalendered and uncalendered sample. The coatings have been applied witha rod bench top coater, Rakelauftragsgerät K-Control-Coater K202, Model624 (Erichsen)/Fabr. No. 57097-4/Rods 1-5 for the control of the liquidflow/Belt dryer 7.0 mmin⁻¹, 150° C.

Mechanical properties of the uncalendered samples were characterized bythe dry pick resistance test which was carried out with coating weightsbetween 7.2 g/m² and 55.97 g/m². The dry pick resistance test provided apick velocity of above 0.5 m/s across all coat weights for both of theuncalendered paper samples. The results for the dry pick resistance testof the tested papers can be gathered from Table 18.

The optical properties of the uncalendered paper samples werecharacterized by brightness, opacity and paper gloss for coating weightsbetween 7.2 g/m² and 55.97 g/m². In addition thereto, the calenderedpaper samples were characterized by the paper gloss for coating weightsbetween 7.2 g/m² and 55.97 g/m². The results for the optical propertiesof the tested papers can be gathered from Tables 19 and 20.

TABLE 18 Dry pick resistance Synteape Coat Pick Sappi base paper Coatingweight velocity Coat weight Pick velocity color [gm⁻²] [ms⁻¹] [gm⁻²][ms⁻¹] 7 7.2 >3 15.6 1.2 21.6 1.8 29.2 0.8 46.4 0.6 56.0 0.8 8 7.4 >317.0 1.0 21.8 >3 29.0 0.6 46.6 0.7 55.5 <0.5

Mechanical properties, like dry pick resistance, and the coat weightscorrespond to rods 1, 3 and 5

TABLE 19 Optical properties Synteape Coat Brightness Paper gloss 75°Coating weight R-457 Opacity Tappi [%] color [gm⁻²] [%] [%] uncalenderedcalendered 7 7.2 90.8 93.0 76.4 98.3 12.3 90.9 93.7 77.9 98.3 21.6 90.994.8 64.5 92.7 35.2 91.0 95.9 82.0 98.9 46.4 91.0 96.5 81.8 96.4 8 7.490.8 93.3 72.0 87.6 12.5 90.8 93.7 72.0 93.2 21.8 90.9 94.6 78.9 92.634.3 90.9 94.8 67.6 91.3 46.6 91.0 96.5 68.6 91.2

The coat weights correspond to rods 1, 2, 3, 4, 5

TABLE 20 Optical properties Sappi base paper Coat Brightness Paper gloss75° Coating weight R-457 Opacity Tappi [%] color [gm⁻²] [%] [%]uncalendered calendered 7 15.6 86.5 91.4 19.2 78.1 21.1 87.0 92.5 21.471.6 29.2 87.6 93.8 22.2 76.1 42.6 88.3 95.6 25.4 80.9 56.0 88.7 96.524.9 75.1 8 17.0 86.9 91.5 18.7 76.4 20.4 87.1 92.5 18.9 77.2 29.0 87.794.0 20.4 80.5 41.9 88.3 95.6 23.1 82.9 55.5 88.8 96.5 24.6 83.5

1. A product obtained by a process comprising the following steps of: a)providing an aqueous pigment material suspension, wherein the pigmentmaterial comprises calcium carbonate; b) providing a starch consistingof at least one anionic starch having a net negative charge; c) mixingthe starch of step b) with the aqueous pigment material suspension ofstep a), wherein the starch is added to the aqueous pigment materialsuspension in an amount from 0.5 to 20 wt.-%, based on the total weightof the dry pigment material in the suspension, d) grinding the aqueouspigment material and starch of step c) to obtain a suspension ofself-binding pigment particles in which the amount of free starch in thesuspension is less than 50 wt.-% based on the total amount of starchadded in step c) and the pigment material surface charge density afterstep d) is in the range of +2.5 μEq/g and −10 μEq/g, wherein grindingstep d) is carried out during and/or after step c) at a temperature from10° C. to 40° C., and wherein grinding is carried out until the fractionof self-binding pigment particles having a particle size of less than 2μm is greater than 20 wt.-% based on the total weight of the pigmentparticles, as measured with a Mastersizer 2000, and e) optionallyconcentrating the self-binding pigment particle suspension obtained instep d).
 2. The product according to claim 1, wherein the pigmentmaterial suspension of step a) comprises calcium carbonate and one ormore of—dolomite, a calcium associated with magnesium, clay, kaolin,titanium dioxide, talc, aluminium hydroxide, mica, synthetic fibers, ornatural fiber.
 3. The product according to claim 1, wherein the pigmentmaterial is a ground natural calcium carbonate, a precipitated calciumcarbonate, a modified calcium carbonate, or any mixture thereof.
 4. Theproduct according to claim 1, wherein the pigment material is a groundnatural calcium carbonate.
 5. The product according to claim 1, whereinthe at least one-anionic starch of step b) is an anionic starchcomprising anionic groups selected from the group consisting of carboxylgroups, carboxymethyl groups, carboxymethyl hydroxypropyl groups,carboxymethyl hydroxyethyl groups, phosphate groups, sulfonate groups,and any mixture thereof.
 6. The product according to claim 1, whereinthe at least one-anionic starch of step b) is an anionic starchcomprising anionic groups selected from the group consisting of carboxylgroups and carboxymethyl groups.
 7. The product according to claim 1,wherein the at least one-anionic starch of step b) is an anionic starchhaving a degree of carboxylation in the range of 0.001 to 0.08.
 8. Theproduct according to claim 1, wherein in step c) the at least oneanionic starch is added to the aqueous pigment material suspension in anamount from 1 to 20 wt.-%, based on the total weight of the dry pigmentmaterial in the aqueous pigment material suspension.
 9. The productaccording to claim 1, wherein the solids content in step c) is adjustedsuch that it is at least 1 wt.-%, based on the total weight of theaqueous pigment material suspension.
 10. The product according to claim1, wherein grinding step d) is carried out during step c).
 11. Theproduct according to claim 1, wherein grinding step d) is carried out ata temperature from 20° C. to 40° C.
 12. The product according to claim1, wherein grinding step d) is carried out until the fraction ofself-binding pigment particles having a particle size of less than 1 μmis greater than 10 wt.-%, and/or until the fraction of self-bindingpigment particles having a particle size of less than 2 μm is greaterthan 20 wt.-%, based on the total weight of the pigment particles. 13.The product according to claim 1, wherein grinding step d) is carriedout until the fraction of self-binding pigment particles having aparticle size of less than 1 μm is greater than 70 wt.-%, and/or untilthe fraction of self-binding pigment particles having a particle size ofless than 2 μm is greater than 80 wt.-%, based on the total weight ofthe pigment particles.
 14. The product according to claim 1, wherein thepigment material in the obtained self-binding pigment particlesuspension has a surface charge density in the range of +2 μEq/g and −8μEq/g.
 15. The product according to claim 1, wherein the pigmentmaterial in the obtained self-binding pigment particle suspension has asurface charge density in the range of +0.5 μEq/g and −6 μEq/g.
 16. Theproduct according to claim 1, wherein the obtained self-binding pigmentparticle suspension has a Brookfield viscosity in the range of 1 to 3500mPas.
 17. The product according to claim 1, wherein grinding step d) iscarried out such that the amount of free starch in the obtainedself-binding pigment particle suspension is less than 45 wt.-%, based onthe total amount of starch added in step c).
 18. The product accordingto claim 1, wherein step e) is performed such that the solids content inthe suspension is at least 45 wt.-%, based on the total weight of theself-binding pigment particle suspension.
 19. The product according toclaim 18, wherein concentration step e) is carried out before or afterstep d).
 20. The product according to claim 1, wherein before or duringor after step c) and/or step d) a dispersing agent is added.